EP2966095A1 - Process of producing resin composition for coating members - Google Patents
Process of producing resin composition for coating members Download PDFInfo
- Publication number
- EP2966095A1 EP2966095A1 EP15181294.8A EP15181294A EP2966095A1 EP 2966095 A1 EP2966095 A1 EP 2966095A1 EP 15181294 A EP15181294 A EP 15181294A EP 2966095 A1 EP2966095 A1 EP 2966095A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymerization
- monomer
- ethylenically unsaturated
- unsaturated bond
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 149
- 239000011248 coating agent Substances 0.000 title claims abstract description 47
- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 title claims abstract description 35
- 230000008569 process Effects 0.000 title description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 213
- 239000000178 monomer Substances 0.000 claims abstract description 126
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 111
- 229920000642 polymer Polymers 0.000 claims abstract description 103
- 150000001875 compounds Chemical class 0.000 claims abstract description 94
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 90
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- 238000000465 moulding Methods 0.000 claims abstract description 18
- 238000004898 kneading Methods 0.000 claims abstract description 16
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 238000009832 plasma treatment Methods 0.000 claims abstract description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 8
- -1 ethylene, propylene, 1-butene Chemical class 0.000 claims description 105
- 239000003963 antioxidant agent Substances 0.000 claims description 73
- 230000003078 antioxidant effect Effects 0.000 claims description 65
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 53
- 229910052698 phosphorus Inorganic materials 0.000 claims description 52
- 239000011574 phosphorus Substances 0.000 claims description 52
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 27
- 239000005977 Ethylene Substances 0.000 claims description 27
- 239000004711 α-olefin Substances 0.000 claims description 25
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 16
- 239000004611 light stabiliser Substances 0.000 claims description 14
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 5
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004383 yellowing Methods 0.000 abstract description 16
- 235000006708 antioxidants Nutrition 0.000 description 71
- 230000000052 comparative effect Effects 0.000 description 58
- 239000005001 laminate film Substances 0.000 description 55
- 238000005469 granulation Methods 0.000 description 47
- 239000000654 additive Substances 0.000 description 38
- 239000003381 stabilizer Substances 0.000 description 32
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 31
- 229920001971 elastomer Polymers 0.000 description 31
- 238000004519 manufacturing process Methods 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000806 elastomer Substances 0.000 description 26
- 229920005672 polyolefin resin Polymers 0.000 description 25
- 238000012360 testing method Methods 0.000 description 25
- 238000010828 elution Methods 0.000 description 23
- 239000000843 powder Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 239000004743 Polypropylene Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 21
- 229920001155 polypropylene Polymers 0.000 description 21
- 230000003179 granulation Effects 0.000 description 20
- 239000010936 titanium Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 230000001070 adhesive effect Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 239000002685 polymerization catalyst Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 230000000996 additive effect Effects 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 15
- 239000002216 antistatic agent Substances 0.000 description 15
- 239000004088 foaming agent Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 14
- 229920000573 polyethylene Polymers 0.000 description 14
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 13
- 150000001336 alkenes Chemical class 0.000 description 13
- 230000006866 deterioration Effects 0.000 description 13
- 239000012442 inert solvent Substances 0.000 description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 13
- 230000000379 polymerizing effect Effects 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000001125 extrusion Methods 0.000 description 12
- 239000000314 lubricant Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910052623 talc Inorganic materials 0.000 description 10
- 239000000969 carrier Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- 239000012456 homogeneous solution Substances 0.000 description 8
- 239000010445 mica Substances 0.000 description 8
- 229910052618 mica group Inorganic materials 0.000 description 8
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000000454 talc Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000002667 nucleating agent Substances 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 239000005022 packaging material Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 230000002411 adverse Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000000873 masking effect Effects 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000010422 painting Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 229920000298 Cellophane Polymers 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 238000009820 dry lamination Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 230000000937 inactivator Effects 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 150000007970 thio esters Chemical class 0.000 description 4
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 0 Cc1cc(CCC(N*)=O)cc(I)c1O Chemical compound Cc1cc(CCC(N*)=O)cc(I)c1O 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003302 alkenyloxy group Chemical group 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000013022 formulation composition Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- GDESWOTWNNGOMW-UHFFFAOYSA-N resorcinol monobenzoate Chemical compound OC1=CC=CC(OC(=O)C=2C=CC=CC=2)=C1 GDESWOTWNNGOMW-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KYKFCSHPTAVNJD-UHFFFAOYSA-L sodium adipate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCC([O-])=O KYKFCSHPTAVNJD-UHFFFAOYSA-L 0.000 description 1
- 239000001601 sodium adipate Substances 0.000 description 1
- 235000011049 sodium adipate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 1
- SNAQARSCIHDMGI-UHFFFAOYSA-M sodium;bis(4-tert-butylphenyl) phosphate Chemical compound [Na+].C1=CC(C(C)(C)C)=CC=C1OP([O-])(=O)OC1=CC=C(C(C)(C)C)C=C1 SNAQARSCIHDMGI-UHFFFAOYSA-M 0.000 description 1
- 239000006076 specific stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ASEHKQZNVUOPRW-UHFFFAOYSA-N tert-butyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C(C)(C)C ASEHKQZNVUOPRW-UHFFFAOYSA-N 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- JHVNMGWNEQGGDU-UHFFFAOYSA-N tert-butyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C(C)(C)C)OCC JHVNMGWNEQGGDU-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- VBRKIFAYTJZAFZ-UHFFFAOYSA-N tert-butyl-dimethoxy-propan-2-ylsilane Chemical compound CO[Si](OC)(C(C)C)C(C)(C)C VBRKIFAYTJZAFZ-UHFFFAOYSA-N 0.000 description 1
- CFWAESPQSRZDQT-UHFFFAOYSA-N tert-butyl-dimethoxy-propylsilane Chemical compound CCC[Si](OC)(OC)C(C)(C)C CFWAESPQSRZDQT-UHFFFAOYSA-N 0.000 description 1
- PSWKAZOCOHMXCW-UHFFFAOYSA-N tert-butyl-ethyl-dimethoxysilane Chemical compound CC[Si](OC)(OC)C(C)(C)C PSWKAZOCOHMXCW-UHFFFAOYSA-N 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- MZHULIWXRDLGRR-UHFFFAOYSA-N tridecyl 3-(3-oxo-3-tridecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCC MZHULIWXRDLGRR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- LTXMJHWSYUANCC-UHFFFAOYSA-N tris(2,4-ditert-butyl-5-methylphenyl) phosphite Chemical compound C1=C(C(C)(C)C)C(C)=CC(OP(OC=2C(=CC(=C(C)C=2)C(C)(C)C)C(C)(C)C)OC=2C(=CC(=C(C)C=2)C(C)(C)C)C(C)(C)C)=C1C(C)(C)C LTXMJHWSYUANCC-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- SGKKYCDALBXNCG-UHFFFAOYSA-N tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-5-methylphenyl] phosphite Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C(=CC(OP(OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)=C(C=2)C(C)(C)C)C)=C1 SGKKYCDALBXNCG-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 238000009821 wax lamination Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910006592 α-Sn Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
- B05D3/141—Plasma treatment
- B05D3/142—Pretreatment
- B05D3/144—Pretreatment of polymeric substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
Definitions
- the present invention relates to a method of producing a laminate film. More particularly, the present invention relates to a method of producing a laminate film which can yield a laminate film having excellent adhesion with a laminate base material and reduce the amount of an anchor coating agent or an adhesive for dry lamination to be used.
- the present invention also relates to a method of producing a resin composition for a coated member which comprises a polymer obtained by polymerization of a monomer having an ethylenically unsaturated bond and a thermoplastic elastomer. More particularly, the present invention relates to a method of producing a resin composition for a coated member, by which a resin composition for a coated member, which shows excellent adhesion with a coating film after a plasma treatment and can have suppressed yellowing, can be produced.
- a laminate film packaging materials utilizing a film made of a thermoplastic resin have been conventionally proposed, and there are known laminate films in which an olefin resin film is laminated on a laminate base material of polyester, polyamide, metallic foil or the like by press-adhesion with heating (heat sealing) or application of an adhesive.
- olefin resins in particular, polyethylene is widely used in the food packaging material applications since it is inexpensive and easily processable and exhibits excellent blocking of water vapor.
- Patent Document 1 a method of producing a laminate film by subjecting the surface of a laminate base material to an anchor coating treatment with an anchoring agent such as a polyurethane or an isocyanate compound and then laminating an ozone-treated olefin resin thereon is proposed.
- an anchoring agent such as a polyurethane or an isocyanate compound
- Patent Document 2 a method of improving the adhesion of a film by subjecting the film to an ozone treatment under a specific condition is disclosed.
- olefin resins have poor stability against heat and light and are thus easily oxidized/degraded when exposed to a high-temperature environment or a strong light, so that the service life required as a plastic product cannot be attained.
- a stabilizer such as a phenolic antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a hydroxylamine compound, a hindered amine compound, an ultraviolet absorber or an acid scavenger is commonly added.
- a phenolic antioxidant is widely utilized because of its high thermostability effect in high-temperature processing.
- Examples of a method of adding a stabilizer to an olefin resin include a method in which an olefin resin obtained by polymerization of an olefin monomer and is mixed with a stabilizer and the resulting mixture is melt-kneaded using a processing equipment such as an extruder to disperse the stabilizer in the olefin resin; and a method in which a stabilizer is added before or during polymerization of an olefin monomer.
- a method of blending an olefin resin and a stabilizer by melt-kneading has a problem in that the stabilizer must be added in an amount more than necessary in order to mitigate the defective dispersion of the stabilizer in the olefin resin.
- Patent Document 3 discloses a production method in which an ⁇ -olefin is polymerized in the presence of a phosphorus-based antioxidant. It is shown that a polymer obtained by polymerizing an ⁇ -olefin in the presence of a phosphorus-based antioxidant can attain superior stabilization effect as compared to a case where a phosphorus-based antioxidant is not used at the time of performing polymerization but is added to a polymer obtained by polymerization of an ⁇ -olefin.
- Patent Document 4 it is shown that, by using a specific phosphorus-based antioxidant at the time of polymerizing an olefin, the polymerization is not inhibited and a polymer in which coloration caused by contact with water is suppressed can be obtained.
- a phenolic antioxidant can provide high thermostability in high-temperature processing of an olefin resin, when a molded article of an olefin resin is immersed in water or a solvent such as alcohol, there are cases where the blended phenolic antioxidant elutes out of the molded article.
- Patent Documents 5 and 6 As a polymerization method in which a phenolic antioxidant is prevented from reducing the catalytic activity of a polymerization catalyst, for example, in Patent Documents 5 and 6, it is shown that inhibition of a polymerization catalyst can be suppressed by adding a phenolic antioxidant masked with an organoaluminum compound before or during polymerization of a monomer having an ethylenically unsaturated bond.
- an olefin resin obtained by polymerization of a monomer having an ethylenically unsaturated bond is inexpensive, has a low specific gravity and a high rigidity, exhibits good moldability and thus can be molded into a large molded article; therefore, such an olefin resin has been increasingly utilized in a variety of applications.
- the use of such an olefin resin has been expanding to structural members and the like, examples of which include exterior parts such as bumpers; interior parts such as instrument panels and trims; engine room interior components such as fan casings; and a variety of module materials.
- such resin compositions used in automobile interior and exterior parts are produced by blending, as required, for example, an olefin resin, an elastomer, an inorganic filler, a pigment such as carbon black, a light stabilizer, an ultraviolet absorber, a hindered phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and a lactone-based antioxidant.
- bumpers are generally provided as unpainted or completely painted products; however, in recent years, in accordance with design requirements, bumpers have been widely provided in a partially unpainted condition. Therefore, it is demanded not only that a resin composition for a bumper have good weathering resistance and good adhesion with a coating film, but also that the bumper and its coating film be not discolored even when exposed to heat, sunlight and the like.
- additives such as an antioxidant, a hindered amine-based light stabilizer and an ultraviolet absorber are blended; however, there is a problem in that such additives blended in an olefin resin are strongly affected by heat and sunlight and diffuse, migrate or bleed out from the resin to a coating film, thereby causing yellowing of the coating film.
- a phenolic antioxidant is converted into quinoline after bleeding out and causes yellowing of a coating film.
- a method of preventing diffusion, migration and bleeding-out of additives by overcoating the coating film with an acryl-melamine system, a two-component urethane system, a polyester-melamine system, a polyester-urethane system or the like can be employed; however, even after the overcoating, a coating color of a high brightness (L value of 60 or higher) may cause yellowing of the coating film under natural environment. Further, by this method, a partially unpainted bumper cannot be obtained.
- Patent Documents 7 and 8 propose methods of inhibiting yellowing of a painted bumper with specific amounts and types of an antioxidant and a light stabilizer.
- Patent Document 9 proposes a method in which specific four types of antioxidants and, as required, a benzoate-based light stabilizer and a hindered amine-based light stabilizer are blended into a polypropylene resin composition which contains a specific propylene-ethylene block copolymer, elastomer and inorganic filler.
- Patent Documents 6, 10 and 11 describe methods in which a phenolic antioxidant masked with an organoaluminum compound is added before or during polymerization of a monomer having an ethylenically unsaturated bond.
- anchor coating agents used in an anchor coating treatment contain, as a diluent, an organic solvent such as ethyl acetate, toluene or methyl ethyl ketone and such anchor coating agents have problems relating to deterioration of work environment due to vaporization of the solvent and disaster prevention, as well as a problem that, if the adhesive is not sufficiently dried, the organic solvent remains in the laminate film and gives odor to its contents.
- an organic solvent such as ethyl acetate, toluene or methyl ethyl ketone
- Patent Document 2 has a problem that, due to the high melt-extrusion temperature, the resin and the blended additives are degraded to cause odor in the contents.
- Patent Documents 5 and 6 the application of the methods to a laminate film is not examined and neither the adhesive property of a laminate film nor the elution of the additives after film formation is examined at all.
- an object of the present invention is to provide a method of producing a laminate film by which a laminate film having excellent adhesion with a laminate base material, in which laminate film the amount of elution of an additive into a solvent is small, can be produced.
- another object of the present invention is to provide a method of producing a resin composition for a coated member, by which a resin composition for a coated member which shows good secondary adhesion with a coating film and good heat-yellowing resistance can be obtained.
- the present inventors also discovered that the above-described problems can be solved by adding a specific stabilizer before or during polymerization of a monomer having an ethylenically unsaturated bond, thereby completing the present invention.
- a stabilized polymer by performing polymerization with an addition of a stabilizer composition to a polymerization catalyst, a polymerization apparatus or a piping thereof.
- This method can omit the step of blending a stabilizer composition by post-polymerization melt-kneading and allows the stabilizer to be uniformly dispersed in the resulting polymer; therefore, the amount of the stabilizer to be blended can be consequently reduced.
- a stabilizer composition containing a phenolic antioxidant could not be added in the polymerization step.
- the present inventors have proposed methods in which, by using a phenolic antioxidant masked with an organoaluminum compound, even when the phenolic antioxidant is added before or during polymerization of a monomer having an ethylenically unsaturated bond, the resulting polymer is stabilized without impairing the activity of a polymerization catalyst even when the phenolic antioxidant is added before or during the polymerization (Patent Documents 6, 10 and 11).
- the method of producing a laminate film according to the present invention is characterized by comprising the step of adding, before or during polymerization of a monomer having an ethylenically unsaturated bond, a phenolic antioxidant represented by the following Formula (1), which is masked with an organoaluminum compound, to at least one of a catalyst system, a polymerization system and a piping, such that the phenolic antioxidant is incorporated in an amount of 0.001 to 0.5 parts by mass with respect to 100 parts by mass of a polymer obtained by the polymerization:
- R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which is optionally branched or an arylalkyl group having 7 to 9 carbon atoms; and R represents an alkyl group having 1 to 30 carbon atoms which is optionally branched, an alkenyl group having 2 to 30 carbon atoms which is optionally branched, a cycloalkyl group
- the method of producing a laminate film according to the present invention further comprise the step of adding, before or during the polymerization of a monomer having an ethylenically unsaturated bond, a phosphorus-based antioxidant to at least one of the catalyst system, the polymerization system and the piping in an amount of 0.001 to 3 parts by mass with respect to 100 parts by mass of the polymer obtained by the polymerization.
- the above-described organoaluminum compound be a trialkylaluminum.
- the laminate film according to the present invention is characterized by being produced by the method of producing a laminate film.
- the method of producing a resin composition for a coated member according to the present invention is a method of producing a resin composition for a coated member, which resin composition comprises a polymer obtained by polymerization of a monomer having an ethylenically unsaturated bond and a thermoplastic elastomer, the method being characterized by comprising the steps of:
- step (B) of the method of producing a resin composition for a coated member according to the present invention it is preferred that the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer be melt-kneaded at a mass ratio, the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond/the thermoplastic elastomer, of 2/1 to 4/1.
- thermoplastic elastomer be obtained by polymerization of a monomer having an ethylenically unsaturated bond, before or during which polymerization of the monomer having an ethylenically unsaturated bond a phenolic antioxidant represented by the above-described Formula (1), which is masked with an organoaluminum compound, is added to at least one of a catalyst system, a polymerization system and a piping.
- the method of producing a resin composition for a coated member according to the present invention further comprise the step of adding, before or during the polymerization of the monomer having an ethylenically unsaturated bond, a phosphorus-based antioxidant to at least one of the catalyst system, the polymerization system and the piping, such that the phosphorus-based antioxidant is incorporated in an amount of 0.001 to 3 parts by mass with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- the above-described organoaluminum compound be a trialkylaluminum.
- the method of producing a coated member according to the present invention is characterized by comprising the step of coating a molded article of a resin composition obtained by the above-described method of producing a resin composition for a coated member. It is preferred that the method of producing a coated member according to the present invention also comprise the step of subjecting the above-described molded article of the resin composition to a plasma treatment before the above-described coating step.
- the coated member according to the present invention is characterized by being produced by the above-described method of producing a coated member and it is preferred that the coated member contain a light stabilizer and a filler.
- a method of producing a laminate film by which a laminate film having excellent adhesion with a laminate base material can be obtained, in which laminate film the amount of elution of an additive into a solvent is small and the amount of an anchoring agent used is reduced, which laminate film can also be utilized in food articles and sanitary goods such as medical supplies, can be provided.
- a method of producing a resin composition for a coated member by which a resin composition for a coated member which shows good secondary adhesion with a coating film and good heat-yellowing resistance can be obtained, can be provided.
- the phenolic antioxidant used in the method of producing a laminate film according to the present invention is a compound represented by the following Formula (1): (wherein, R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which is optionally branched or an arylalkyl group having 7 to 9 carbon atoms; and R represents an alkyl group having 1 to 30 carbon atoms which is optionally branched, an alkenyl group having 2 to 30 carbon atoms which is optionally branched, a cycloalkyl group having 3 to 12 carbon atoms which is optionally substituted or an aryl group having 6 to 18 carbon atoms which is optionally substituted).
- R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which is optionally branched or an arylalkyl group having 7 to 9 carbon atoms; and R represents an alkyl group having 1 to 30 carbon atoms which is optionally branched
- Examples of the alkyl group having 1 to 5 carbon atoms which is optionally branched and represented by R 1 and R 2 in the above-described Formula (1) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, sec-pentyl group and tert-pentyl group; however, the alkyl group is particularly preferably a tert-butyl group since it has good effect of stabilizing the phenolic antioxidant.
- Examples of the arylalkyl group having 7 to 9 carbon atoms which is represented by R 1 and R 2 in the above-described Formula (1) include benzyl and 1-methyl-1-phenylethyl.
- alkyl group having 1 to 30 carbon atoms which is optionally branched and represented by R in the above-described Formula (1) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, isobutyl group, pentyl group, isopentyl group, t-pentyl group, hexyl group, heptyl group, n-octyl group, isooctyl group, t-octyl group, nonyl group, isononyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group; however, in the present invention, an alkyl group having 12 to 24 carbon
- the phenolic antioxidant When the alkyl group has less than 12 carbon atoms, the phenolic antioxidant may be easily vaporized, while when the alkyl group has more than 24 carbon atoms, the ratio of phenol relative to the molecular weight of the phenolic antioxidant is decreased, so that the stabilizing effect may be reduced.
- alkyl groups are also optionally interrupted by an oxygen atom, a sulfur atom or the below-described aryl group, and the hydrogen atoms of the alkyl groups are also optionally substituted with a hydroxy group, a cyano group, an alkenyl group, a chain aliphatic group such as an alkenyloxy group, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, isoxazole, isothiazole, pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, morpholine, 2H-pyran, 4H-pyran, phenyl, biphenyl, triphenyl, naphthalene, anthracene, pyrrolidine, pyrindine, indolizine, indole, isoindole, indazole, purine, quinolizine,
- the alkenyl group having 2 to 30 carbon atoms which is optionally branched and may be represented by the above-described R is the above-described alkyl group into which a carbon-carbon double bond is introduced.
- an alkenyl group having 12 to 24 carbon atoms is particularly preferred.
- Examples of the cycloalkyl group having 3 to 12 carbon atoms which is optionally substituted and represented by R in the above-described Formula (1) include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group and cyclodecyl group.
- the hydrogen atoms of the cycloalkyl group are optionally substituted with an alkyl group, an alkenyl group, an alkenyloxy group, a hydroxy group or a cyano group, and the alkyl group is also optionally interrupted by an oxygen atom or a sulfur atom.
- Examples of the aryl group having 6 to 18 carbon atoms which is optionally substituted and represented by R in the above-described Formula (1) include phenyl group, methylphenyl group, butylphenyl group, octylphenyl group, 4-hydroxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-t-butylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, phenanthryl group, benzyl group, phenylethyl group and 1-phenyl-1-methylethyl group.
- the hydrogen atoms of the aryl group are optionally substituted with an alkyl group, an alkenyl group, an alkenyloxy group, a hydroxy group or a cyano group, and the alkyl group is also optionally interrupted by an oxygen atom or a sulfur atom.
- the phenolic antioxidant represented by the above-described Formula (1) which is masked with an organoaluminum compound is added in an amount of 0.001 to 0.5 parts by mass, preferably 0.001 to 0.3 parts by mass, with respect to 100 parts by mass of the polymer obtained by the polymerization.
- the amount of the phenolic antioxidant is less than 0.001 parts by mass, the effect of the addition may not be attained.
- the phenolic antioxidant can be added in an amount of greater than 0.5 parts by mass; however, such an amount is economically disadvantageous because it causes the resulting polymer to be colored and the effect of the addition is limited.
- a method of adding the phenolic antioxidant represented by the above-described Formula (1) which is masked with an organoaluminum compound there is no particular restriction.
- suitable mode thereof include one in which the masked phenolic antioxidant is added and mixed in at least one of a catalyst feed tank, a polymerization apparatus and a piping of the production line.
- the above-described masking can be performed by mixing and stirring an organoaluminum compound and the phenolic antioxidant in an inert solvent. By the mixing and stirring, the hydrogen of the phenolic hydroxyl group of the phenolic antioxidant is substituted with the organoaluminum compound.
- the above-described phenolic antioxidant and organoaluminum compound may be mixed with stirring prior to being added to at least one of the catalyst system, the polymerization system and the piping. Alternatively, the phenolic antioxidant and the organoaluminum compound may be added and mixed separately in at least one of the catalyst system, the polymerization system and the piping.
- the masked phenolic antioxidant may be used as is; however, in cases where the by-produced compound inhibits the polymerization, it is preferred to remove the compound by vacuum distillation or the like before adding the masked phenolic antioxidant to at least one of the catalyst system, the polymerization system and the piping.
- the above-described masked phenolic antioxidant be capable of regenerating phenol by undergoing a reaction with a hydrogen-donating compound such as water, an alcohol or an acid, which is added as a deactivation treatment of the polymerization catalyst after the polymerization.
- a hydrogen-donating compound such as water, an alcohol or an acid
- organoaluminum compound examples include alkylaluminums and alkylaluminum hydrides, and the organoaluminum compound is preferably an alkylaluminum, particularly preferably a trialkylaluminum.
- the trialkylaluminum examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum, and these compounds may be used individually or in combination as a mixture.
- an aluminoxane obtained by a reaction between an alkylaluminum or an alkylaluminum hydride and water can also be used in the same manner.
- the mixing ratio of the organoaluminum compound and the phenolic antioxidant represented by the above-described Formula (1) be, in terms of mass ratio, 1/5 to 100/1.
- the ratio of the organoaluminum compound is lower than 1/5, the excessive amount of the phenolic antioxidant may adversely affect the catalyst activity, while when the ratio is higher than 100/1, an aluminum compound remains in the resulting polymer after the polymerization and this may cause deterioration in the physical properties of the polymer or affect the component ratio of the catalyst metal, making it unable to perform the desired polymerization.
- Examples of the above-described inert solvent include aliphatic and aromatic hydrocarbon compounds.
- Examples of the aliphatic hydrocarbon compounds include saturated hydrocarbon compounds such as n-pentane, n-hexane, n-heptane, n-octane, isooctane and refined kerosene; and cyclic saturated hydrocarbon compounds such as cyclopentane, cyclohexane and cycloheptane.
- Examples of the aromatic hydrocarbon compounds include benzene, toluene, ethylbenzene, xylene and gasoline fractions. Among these compounds, n-hexane, n-heptane or a gasoline fraction is preferably used.
- the concentration of the trialkylaluminum salt in the inert solvent is preferably 0.001 to 0.5 mol/L, particularly preferably 0.01 to 0.1 mol/L.
- the production method according to the present invention further comprise the step of adding, before or during the polymerization of the monomer having an ethylenically unsaturated bond, a phosphorus-based antioxidant to at least one of the catalyst system, the polymerization system and the piping in an amount of 0.001 to 3 parts by mass with respect to 100 parts by mass of the polymer obtained by the polymerization.
- Examples of the phosphorus-based antioxidant used in the present invention include known phosphorus-based antioxidants such as triphenyl phosphite, trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,4-di-tert-butyl-5-methylphenyl)phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di
- a phosphorus-based antioxidant which does not adversely affect the polymerization even when it is added before the polymerization of propylene monomer, such as tris(2,4-di-tert-butylphenyl)phosphite, is preferred.
- the phosphorus-based antioxidant is added in an amount of 0.001 to 3 parts by mass, preferably 0.005 to 0.5 parts by mass, with respect to 100 parts by mass of the polymer obtained by the polymerization of a monomer having an ethylenically unsaturated bond.
- the amount is less than 0.001 parts by mass, the effect of the addition may not be attained.
- the phosphorus-based antioxidant can be added in an amount of 3 parts by mass or greater; however, such an amount is economically disadvantageous because the effect of the addition is small.
- the phosphorus-based antioxidant is preferably mixed with the above-described inert solvent before being added, and the phosphorus-based antioxidant may also be mixed in advance with the inert solvent along with the phenolic antioxidant represented by the above-described Formula (1).
- the phosphorus-based antioxidant may be mixed with the inert solvent and added to the polymerization system, the catalyst system or the piping, separately from the phenolic antioxidant represented by the Formula (1).
- the phenolic antioxidant represented by the above-described Formula (1) which is masked with an organoaluminum compound and the above-described phosphorus-based antioxidant are added in a total amount of preferably 0.001 to 3 parts by mass, more preferably 0.001 to 0.5 parts by mass, with respect to 100 parts by mass of the polymer obtained in the polymerization step.
- Examples of the above-described monomer having an ethylenically unsaturated bond include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcycloalkane, styrene and derivatives of these monomers.
- the monomer used in the present invention which has an ethylenically unsaturated bond may either be a single type of monomer or a combination of two or more types of monomers, and it is preferably ethylene or a combination of ⁇ -olefin monomers.
- the monomer may also be, for example, ethylene by itself, a combination of ethylene and propylene, a combination of ethylene, propylene and butene, or a combination of an ⁇ -olefin monomer and a non-conjugated diene monomer.
- any conventionally used method can be employed.
- a method of performing polymerization in a liquid phase in the presence of an inert solvent such as an aliphatic hydrocarbon (e.g., butane, pentane, hexane, heptane or isooctane), an alicyclic hydrocarbon (e.g., cyclopentane, cyclohexane or methylcyclohexane), an aromatic hydrocarbon (e.g., toluene, xylene or ethylbenzene), a gasoline fraction or a hydrogenated diesel fraction; a polymerization method in which a liquefied monomer itself is used as a medium; a method of performing polymerization in a gas phase where substantially no liquid phase is present, such as an inert gas atmosphere of nitrogen or the like; or a combination of two or more of these
- an active hydrogen compound, a particulate carrier, an organoaluminum compound, an ion-exchanging layered compound, an inorganic silicate or a catalyst component other than the above-described polymerization catalyst, such as a carrier may also be incorporated in such an amount which does not inhibit the polymerization.
- a continuous reaction vessel installed in an existing polymerization equipment can be used as is.
- the above-described polymerization catalyst is not particularly restricted and any known polymerization catalyst can be employed.
- Examples thereof include compounds of transition metals belonging to one of the groups 3 to 11 of the periodic table (such as titanium, zirconium, hafnium, vanadium, iron, nickel, lead, platinum, yttrium and samarium).
- the polymerization catalyst include Ziegler catalysts; Ziegler-Natta catalysts composed of a titanium-containing solid transition metal component and an organic metal component; Brookhart catalysts, which are compounds in which a hetero atom of nitrogen, oxygen, sulfur, phosphorus or the like is bound to a transition metal belonging to one of the groups 4 to 10 of the periodic table; and metallocene catalysts composed of a transition metal compound belonging to one of the groups 4 to 6 of the periodic table, which has at least one cyclopentadienyl skeleton, and a co-catalyst component.
- an electron-donating compound is preferably employed since a high-quality polymer can be obtained.
- Ziegler catalysts include those catalysts that are produced by subjecting a titanium trichloide or titanium trichloride composition, which is obtained by reduction of titanium tetrachloride with organoaluminum or the like, to a treatment with an electron-donating compound and then activating the resultant (see, for example, Japanese Unexamined Patent Application Publication Nos.
- catalysts composed of a titanium trichloride composition, which is obtained by reducing titanium tetrachloride with an organoaluminum compound and then treating the resultant with a variety of electron donors and electron acceptors, an organoaluminum compound and an aromatic carboxylic acid ester (see, for example, Japanese Unexamined Patent Application Publication Nos. S56-100806 , S56-120712 and S58-104907 ); and supported-type catalysts composed of titanium tetrachloride and a variety of electron donors that are supported on magnesium halide (see, for example, Japanese Unexamined Patent Application Publication Nos. S57-63310 , S58-157808 , S58-83006 , S58-5310 , S61-218606 , S63-43915 and S63-83116 ).
- metallocene catalysts examples include the transition metal metallocene catalyst described in Japanese Unexamined Patent Application Publication No. H9-12621 ; and those transition metal metallocene catalysts primarily used in polymerization of polypropylene, which are described in Japanese Unexamined Patent Application Publication Nos.
- H5-043616 H5-295022 , H5-301917 , H6-239914 , H6-239915 , H6-239917 , H7-082311 , H7-228621 , H7-330820 , H8-059724 , H8-085707 , H8-085708 , H8-127613 , H10-226712 , H10-259143 , H10-265490 , H11-246582 , H11-279189 , H11-349633 , 2000-229990 , 2001-206914 , 2002-37795 , 2002-194015 and 2002-194016 , Japanese Translated PCT Patent Application Laid-open No. 2002-535339 , WO 99/37654 , WO 99/45014 and WO 00/8036 .
- Examples of the above-described electron-donating compounds include ether-based compounds, ester-based compounds, ketone-based compounds and alkoxysilane-based compounds. These electron-donating compounds may be added individually, or a plurality thereof may be added as required.
- ether-based compounds examples include diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene oxide, tetrahydrofuran, 2,2,5,5-tetramethyl tetrahydrofuran and dioxane.
- ester-based compounds examples include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, ethyl phenylacetate, methyl benzoate, ethyl benzoate, phenyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, methyl methoxybenzoate, ethyl methoxybenzoate, methyl methacrylate, ethyl methacrylate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipropyl phthalate, dibutyl phthalate, dipropyl phthalate, dibutyl phthal
- ketone-based compounds examples include acetone, diethyl ketone, methylethyl ketone and acetophenone.
- alkoxysilane-based compounds include tetramethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, phenyltrimethoxysilane, cyclohexyltrimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butyl-n-propyldimethoxysilane, t-butylisopropyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohe
- the type of the above-described carrier is not restricted and examples thereof include inorganic carriers such as inorganic oxides and organic carriers such as porous polyolefins. A plurality of these carriers may also be used in combination.
- examples of the above-described inorganic carriers include silica, alumina, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium oxide and zinc oxide.
- examples of other inorganic carriers include magnesium halides such as magnesium chloride and magnesium bromide; magnesium alkoxides such as magnesium ethoxide; and ion-exchanging layered compounds.
- ion-exchanging layered compounds refer to those compounds having a crystalline structure in which the surfaces constituted by ionic bonds and the like are laminated in parallel with each other through week bonding force and contain exchangeable ions.
- Specific examples of such ion-exchanging layered compound include kaolin, bentonite, talc, kaolinite, vermiculite, montmorillonite, mica, ⁇ -Zr(HAsO 4 ) 2 ⁇ H 2 O, ⁇ -Zr(HPO 4 ) 2 ⁇ H 2 O, ⁇ -Sn(HPO 4 ) 2 ⁇ H 2 O and ⁇ -Ti(NH 4 PO 4 ) 2 ⁇ H 2 O.
- organic carriers examples include polyesters such as polyethylenes, polypropylenes, polystyrenes, ethylene-butene copolymers, ethylenepropylene copolymers, polymethacrylates, polyacrylates, polyacrylonitriles, polyamides, polycarbonates and polyethylene terephthalates; and polyvinyl chlorides. These organic carriers may also be cross-linked as in the case of, for example, a styrene-divinylbenzene copolymer. Further, catalysts chemically bound to these organic carriers can be used as well.
- These carriers have a particle size (volume average) in the range of usually 0.1 to 300 ⁇ m, preferably 1 to 200 ⁇ m, more preferably 10 to 100 ⁇ m.
- the particle size of the carrier should be selected in accordance with the desired particle shape.
- the above-described carrier usually has a pore volume of 0.1 to 5 cm 2 /g, preferably 0.3 to 3 cm 2 /g.
- the pore volume can be measured by, for example, a BET method or mercury porosimetry.
- organoaluminum compound examples include the same ones as those exemplified for the organoaluminum compound used in the masking of the above-described phenolic antioxidant represented by the Formula (1).
- additive(s) that are normally used in a polymer obtained from a monomer having an ethylenically unsaturated bond may also be blended.
- the additives may be added before or at the time of polymerizing the monomer having an ethylenically unsaturated bond, as long as the additives do not inhibit the polymerization.
- other additives may be mixed with the above-described polymer in an amount appropriate for the intended purpose and the resulting mixture can then be granulated and molded by melt-kneading using a molding apparatus such as an extruder.
- antioxidants examples include phenolic antioxidants, phosphorus-based antioxidants, thioester-based antioxidants, ultraviolet absorbers, hindered amine compounds, heavy metal inactivators, nucleating agents, flame retardants, metallic soaps, hydrotalcites, fillers, lubricants, antistatic agents, pigments, dyes and plasticizers.
- phenolic antioxidant is different from the one represented by the above-described Formula (1).
- examples of such phenolic antioxidant include 2,6-dit-butyl-4-ethylphenol, 2-t-butyl-4,6-dimethylphenol, styrenated phenol, 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-thiobis-(6-t-butyl-4-methylphenol), 2,2'-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2-methyl-4,6-bis(octylsulfanylmethyl)phenol, 2,2'-isobutylidenebis(4,6-dimethylphenol), iso-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-(3,5-diy
- the phenolic antioxidant used as the above-described other additive is added in an amount of 0.001 to 5 parts by mass, more preferably 0.001 to 0.5 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- Examples of the phosphorus-based antioxidant used as the above-described other additive include the same ones as those compounds exemplified in the above as the phosphorus-based antioxidant to be added.
- the above-described phosphorus-based antioxidant is used in an amount of preferably 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the above-described polymer.
- thioester-based antioxidant examples include tetrakis[methylene-3-(laurylthio)propionate]methane, bis(methyl-4-[3-n-alkyl(C 12/C14)thiopropionyloxy]5-t-butylphenyl)sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl/stearyl thiodipropionate, 4,4'-thiobis(6-t-butyl-m-cresol), 2,2'-thiobis(6-t-butyl-p-cresol) and distearyl-disulfide.
- the thioester-based antioxidant is used in an amount of preferably 0.001 to 0.3 parts by mass, more preferably 0.01 to 0.3 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- Examples of the above-described ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxyphenyl)benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2-(2-
- the above-described ultraviolet absorber is used in an amount of 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- hindered amine-based light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) ⁇ di(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) ⁇ di(tridecyl)-1
- the above-described hindered amine-based light stabilizer is used in an amount of preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- Examples of the above-described heavy metal inactivator include salicylamide-1,2,4-triazol-3-yl, bis-salicylic acid hydrazide, dodecanedioyl-bis(2-(2-hydroxybenzoyl)hydrazide) and bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid)hydrazide.
- the heavy metal inactivator is used in an amount of preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- nucleating agent examples include metal carboxylates such as sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate and 2-sodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; metal phosphates such as sodium-bis(4-tert-butylphenyl)phosphate, sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate and lithium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate; polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol and bis(dimethylbenzylidene)sorbitol; and amide compounds such as N,N',N"-tris[2-methylcyclohexyl]-1,2,3-propane
- the above-described nucleating agent is used in an amount of 0.001 to 10 parts by mass, more preferably 0.005 to 5 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- Examples of the above-described flame retardant include aromatic phosphates such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-xylenyl phosphate and resorcinol-bis(diphenylphosphate); phosphonates such as divinyl phenyl phosphonate, diallyl phenyl phosphonate and (1-butenyl)phenylphosphonate; phosphinates such as phenyl diphenylphosphinate, methyl diphenylphosphinate and 9,10-dihydro-9-oxa-10-phosphaphenanthlene-10-oxide derivatives; phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene; phosphorus-based flame retardants such as melamine phosphate, melamine pyro
- the above-described flame retardant is used in an amount of preferably 1 to 70 parts by mass, more preferably 10 to 30 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- Examples of the above-described filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fibers, clays, dolomite, mica, silica, alumina, potassium titanate whiskers, wollastonite and fibrous magnesium oxysulfate.
- a filler having an average particle size (in the case of a spherical or flat filler) or an average fiber diameter (in the case of a needle-form or fibrous filler) of 5 ⁇ m or less is preferred.
- the amount of the above-described filler to be used can be set as appropriate in a range where the present invention is not adversely affected.
- the above-described lubricant is added for the purpose of imparting the surface of the resulting molded article with lubricity and improving its damage-preventing effect.
- examples of such lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; and saturated fatty acid amides such as behenic acid amide and stearic acid amide. These lubricants may be used individually, or two or more thereof may be used in combination.
- the above-described lubricant is added in an amount of 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass, with respect to 100 parts by mass of the above-described polymer.
- the amount is less than 0.03 parts by mass, the desired lubricity may not be attained, while when the amount is greater than 2 parts by mass, the lubricant component may bleed out to the surface of the resulting molded article of the polymer and/or cause deterioration in the physical properties thereof.
- the above-described antistatic agent is added for the purpose of reducing the electrostatic property of the resulting molded article and preventing adhesion of dusts caused by electrostatic charge.
- the antistatic agent include cationic, anionic and non-ionic antistatic agents. Preferred examples include polyoxyethylene alkylamines, polyoxyethylene alkyl amides, fatty acid esters thereof and glycerin fatty acid esters. These antistatic agents may be used individually, or two or more thereof may be used in combination. Further, the antistatic agent is added in an amount of preferably 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass, with respect to 100 parts by mass of the above-described polymer. When the amount of the antistatic agent is excessively small, the antistatic effect becomes insufficient, while when the amount is excessively large, the antistatic agent may bleed out to the surface and/or cause deterioration in the physical properties of the polymer.
- the method of producing a laminate film according to the present invention is characterized by comprising the step of adding, before or during polymerization of a monomer having an ethylenically unsaturated bond, a phenolic antioxidant represented by the above-described Formula (1), which is masked with an organoaluminum compound, to at least one of a catalyst system, a polymerization system and a piping, such that the phenolic antioxidant is incorporated in an amount of 0.001 to 0.5 parts by mass with respect to 100 parts by mass of a polymer obtained by the polymerization.
- a phenolic antioxidant represented by the above-described Formula (1) which is masked with an organoaluminum compound
- a phenolic antioxidant other than the specific phenolic antioxidant according to the present invention exhibits poor stabilization effect when added at the time of polymerization; therefore, such a phenolic antioxidant is required to be added in a large amount. Consequently, the antioxidant bleeds out to inhibit the adhesion of a laminate film.
- the resulting polymer can be molded into a laminate film by a known method.
- Examples of a method of processing the above-described polymer into a laminate film include a method in which the above-described polymer is molded into films and a laminate film is produced by laminating the films with each other or by laminating the film(s) with a laminate base material. Further, as required, the above-described polymer may also be processed into a laminate film having three or more layers.
- Examples of the above-described laminate base material include those that are normally used by being adhered with a film, such as polymers having a film-forming capability, papers, nonwoven fabrics, metal foils (e.g., aluminum foils), metal-deposited films (e.g., silicon oxide-deposited films and aluminum-deposited films) and cellophanes.
- a film such as polymers having a film-forming capability, papers, nonwoven fabrics, metal foils (e.g., aluminum foils), metal-deposited films (e.g., silicon oxide-deposited films and aluminum-deposited films) and cellophanes.
- the thickness of the above-described laminate base material is not particularly restricted and can be selected as appropriate in accordance with the purpose thereof.
- the thickness of the above-described laminate base material may be generally about 5 to 50 ⁇ m.
- the laminate base material may be subjected to a surface treatment such as an ozone treatment, a corona discharge treatment or a flame treatment.
- polymers having a film-forming capability examples include olefin-based copolymers such as high-density polyethylenes, medium/low-density polyethylenes, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, ionomers, polypropylenes, poly-1-butene and poly-4-methyl1-pentene; vinyl-based polymers such as polyvinyl chlorides, polyvinylidene chlorides, polystyrenes, polyacrylates and polyacrylonitriles; polyamides such as nylons and polymetaxylylene adipamide; polyesters such as polyethylene terephthalates, polyethylene isophthalates, polybutylene terephthalates and polyethylene naphthalates; polyvinyl alcohols; ethylene-vinyl alcohol copolymers; and polycarbonates. Further, films obtained by molding these polymers may also be stretched uniaxially or biaxially.
- polyethylenes are preferred.
- a linear low-density polyethylene (LLDPE) is preferred since it has excellent heat-seal property and heat resistance and exhibits resistance to bending and rubbing when made into a packaging material.
- the thickness of the laminate film produced by the production method according to the present invention is not particularly restricted and can be selected as appropriate in accordance with the purpose thereof.
- the thickness of the laminate film may be generally 10 to 200 ⁇ m.
- a dry lamination method for example, a dry lamination method, an extrusion lamination method, a hot-melt lamination method, a wet lamination method, a wax lamination method or a thermal lamination method can be employed.
- the above-described dry lamination method is a method in which an adhesive diluted with an organic solvent to an appropriate viscosity is coated onto a film and this film is dried and then laminated with the other film by press-adhesion.
- the adhesive one composed of a base agent and a curing agent is commonly used.
- the base agent examples include ester compounds composed of isophthalic acid, adipic acid, sebacic acid or the like and ethylene glycol, neopentyl glycol, 1,6-hexane diol or the like; polyester-urethane diol resins composed of isophorone diisocyanate, xylylene diisocyanate, or hexamethylene diisocyanate; silane coupling agents; and epoxy-resin containing agents.
- the curing agent examples include those that are composed of trimethylolpropane and isophorone diisocyanate, xylylene diisocyanate or hexamethylene diisocyanate.
- the base agent and the curing agent are not restricted to the ones exemplified in the above and they can be selected as appropriate in accordance with the intended purpose of providing heat resistance, or chemical resistance.
- extrusion lamination method examples include a method of producing a poly-laminate by coating molten polyethylene onto one side of a film and a method of producing a poly-sandwich laminate by pouring molten polyethylene between two films.
- the molten polyethylene serves as an adhesive; however, polypropylene may be used in place of polyethylene.
- an anchor coating agent is applied to the surface of a film, a paper and a thick film can also be easily laminated thereon.
- anchor coating agent examples include adhesives for epoxy resins, such as carboxylic acid anhydride-modified polyolefins, isocyanate-based resins, organic titanate-based resins and polyethylene imine-based resins and polybutadiene-based resins; however, an isocyanate-based resin having excellent water resistance, moisture resistance and boiling resistance is preferably employed.
- epoxy resins such as carboxylic acid anhydride-modified polyolefins, isocyanate-based resins, organic titanate-based resins and polyethylene imine-based resins and polybutadiene-based resins
- an isocyanate-based resin having excellent water resistance, moisture resistance and boiling resistance is preferably employed.
- the above-described hot-melt lamination method is a method in which an adhesive or the like, which is adjusted by heating to have an appropriate viscosity, is coated onto a film and this film press-adhered.
- This method is advantageous in that it includes no drying step and the resulting laminate can be used immediately after being cooled; however, the method has drawbacks in that, for example, the resulting laminate is poor in heat resistance and strength.
- the above-described wet lamination method is a method of laminating using a water-soluble or emulsion-type adhesive.
- the water-soluble or emulsion-type adhesive include water-soluble vinylons and vinyl acetate-based emulsions.
- the above-described thermal lamination method is a method capable of adhering the film only by press-adhesion with application of heat thereto. This method is advantageous in that it does not require an adhesive, a solvent and the like to be used; however, since the resulting laminate has poor heat resistance as a packaging material, the use thereof is limited.
- the use of the laminate film obtained by the production method of the present invention is not particularly restricted and the laminate film can be generally utilized in those applications where a laminate film is conventionally used.
- Examples thereof include the uses as food packaging materials in the form of a laminate film having an olefin film highly resistant to water as an outer layer or a laminate obtained by laminating a low-density polyethylene, a medium-density polyethylene, an ethylene-vinyl acetate copolymer or the like. Further, in cases where the laminate film is utilized as a boil-in-bag pouch or a retort pouch packaging material, for example, an oxygen impermeable film such as an aluminum foil is laminated as an inner layer.
- the method of producing a resin composition for a coated member according to the present invention is characterized by comprising the steps (A) and (B).
- steps such as the step of preparing a catalyst, the step of feeding a monomer which is a starting material, the step of polymerizing the monomer and the step of recovering the resulting polymer, those method that are known in the method of polymerization a monomer having an ethylenically unsaturated bond can be employed.
- steps will each be described in detail.
- the term "coated member” used in the present invention refers to a member obtained by coating a molded article of a resin composition.
- the step (A) is a step of adding, before or during polymerization of a monomer having an ethylenically unsaturated bond, a phenolic antioxidant represented by the above-described Formula (1), which is masked with an organoaluminum compound, to at least one of a catalyst system, a polymerization system and a piping, such that the above-described phenolic antioxidant is incorporated in an amount of 0.001 to 0.5 parts by mass with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and a thermoplastic elastomer.
- the phenolic antioxidant represented by above-described Formula (1) which is masked with an organoaluminum compound, is added such that the amount of the phenolic antioxidant (that is, the amount of the phenolic antioxidant by itself prior to being masked) becomes preferably 0.001 to 0.5 parts by mass, more preferably 0.001 to 0.3 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and a thermoplastic elastomer.
- the amount of the phenolic antioxidant is less than 0.001 parts by mass, a desired stabilization effect may not be attained, while when the amount is greater than 0.5 parts by mass, the phenolic antioxidant may bleed out to the surface of the resulting molded article to cause the outer appearance.
- the phenolic antioxidant represented by above-described Formula (1) which is masked with an organoaluminum compound, is added before or during polymerization of a monomer performed to obtain a thermoplastic elastomer
- the phenolic antioxidant is added such that the total amount of the phenolic antioxidant added in the step (A) and in the synthesis of the thermoplastic elastomer is in the above-described range.
- a method of adding the phenolic antioxidant represented by the above-described Formula (1) which is masked with an organoaluminum compound there is no particular restriction.
- suitable mode thereof include one in which the masked phenolic antioxidant is added and mixed in at least one of a catalyst feed tank, a polymerization apparatus and a production line.
- the above-described masking can be performed by mixing and stirring an organoaluminum compound and the phenolic antioxidant in an inert solvent. By the mixing and stirring, the hydrogen of the phenolic hydroxyl group of the phenolic antioxidant is substituted with the organoaluminum compound.
- the above-described phenolic antioxidant and organoaluminum compound may be mixed with stirring prior to being added to at least one of the catalyst system, the polymerization system and the piping. Alternatively, the phenolic antioxidant and the organoaluminum compound may be added and mixed separately in at least one of the catalyst system, the polymerization system and the piping.
- the masked phenolic antioxidant may be used as is; however, in cases where the by-produced compound has an effect, it is preferred to remove the compound by vacuum distillation or the like before adding the masked phenolic antioxidant to at least one of the catalyst system, the polymerization system and the piping.
- the above-described masked phenolic antioxidant be capable of undergoing a reaction with a hydrogen-donating compound such as water, an alcohol or an acid, which is added as a deactivation treatment of the polymerization catalyst after the polymerization, and be thereby regenerated.
- a hydrogen-donating compound such as water, an alcohol or an acid
- organoaluminum compound examples include the same ones as those exemplified in the above.
- the mixing ratio of the organoaluminum compound and the phenolic antioxidant represented by the above-described Formula (1) be, in terms of mass ratio, 1/5 to 100/1.
- the ratio of the organoaluminum compound is lower than 1/5, the excessive amount of the phenolic antioxidant may adversely affect the catalyst activity, while when the ratio is higher than 100/1, an aluminum compound remains in the resulting polymer after the polymerization and this may cause deterioration in the physical properties of the polymer or affect the component ratio of the catalyst metal, making it unable to perform the desired polymerization.
- the concentration of the organoaluminum compound in the inert solvent is in the range of preferably 0.001 to 0.5 mol/L, particularly preferably 0.01 to 0.1 mol/L.
- the method of producing a resin composition for a coated member according to the present invention further comprise the step of adding, before or during the polymerization of the monomer having an ethylenically unsaturated bond, a phosphorus-based antioxidant to at least one of the catalyst system, the polymerization system and the piping.
- a phosphorus-based antioxidant represented by the above-described Formula (1) and the phosphorus-based antioxidant may be added separately, or they may be mixed in advance before being added.
- the phosphorus-based antioxidant may also be added at the time of the polymerization of the below-described thermoplastic elastomer (before or during the polymerization of a monomer).
- Examples of the above-described phosphorus-based antioxidant include the same ones as those exemplified in the above.
- the above-described phosphorus-based antioxidant is used in an amount of preferably 0.001 to 3 parts by mass, more preferably 0.005 to 0.5 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- the phosphorus-based antioxidant is preferably mixed with the above-described inert solvent; however, the phosphorus-based antioxidant may also be mixed in advance with the inert solvent along with the phenolic antioxidant represented by the above-described Formula (1). Alternatively, the phosphorus-based antioxidant may be mixed with the inert solvent and added to the polymerization system, the catalyst system or the piping, separately from the phenolic antioxidant represented by the Formula (1).
- Examples of the above-described monomer having an ethylenically unsaturated bond include the same ones as those exemplified in the above.
- the monomer to be used which has an ethylenically unsaturated bond may either be a single type of monomer or a combination of two or more types of monomers, and it is preferably ethylene or a combination of ⁇ -olefin monomers.
- the monomer may also be, for example, ethylene by itself, a combination of ethylene and propylene, a combination of ethylene, propylene and butene, or a combination of an ⁇ -olefin monomer and a non-conjugated diene monomer.
- Examples of a method of performing the polymerization reaction of the monomer having an ethylenically unsaturated bond include the same ones as those exemplified in the above.
- a continuous reaction vessel installed in an existing polymerization equipment can be used as is.
- Examples of a polymerization catalyst used in the above-described polymerization reaction include the same ones as those exemplified in the above.
- the polymerization reaction may also be performed in the presence of an active hydrogen compound, an organoaluminum compound, an ion-exchanging layered compound, an inorganic silicate or a catalyst component other than the above-described polymerization catalyst, such as a carrier, in such an amount which does not inhibit the polymerization.
- Examples of the above-described carrier include the same ones as those exemplified in the above.
- Examples of the above-described ion-exchanging layered compound include the same ones as those exemplified in the above.
- Examples of the above-described organic carrier include the same ones as those exemplified in the above.
- the carrier has a particle size (volume average) in the range of usually 0.1 to 300 ⁇ m, preferably 1 to 200 ⁇ m, more preferably 10 to 100 ⁇ m.
- the particle size of the carrier is preferably selected in accordance with the desired particle shape.
- the above-described carrier usually has a pore volume of 0.1 to 5 cm 2 /g, preferably 0.3 to 3 cm 2 /g.
- the pore volume can be measured by, for example, a BET method or mercury porosimetry.
- organoaluminum compound examples include the same ones as those exemplified for the organoaluminum compound used to mask the phenolic antioxidant represented by the Formula (1).
- additive(s) that are normally used in a polymer obtained from a monomer having an ethylenically unsaturated bond may also be blended.
- the additives may be added at the time of polymerizing the monomer having an ethylenically unsaturated bond, as long as the additives do not inhibit the polymerization.
- other additives may be mixed with the above-described polymer in an amount appropriate for the intended purpose and the resulting mixture can then be granulated and molded by melt-kneading using a molding apparatus such as an extruder.
- the step (B) is a step of melt-kneading the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond with the thermoplastic elastomer.
- the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer be melt-kneaded at a mass ratio (the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond/the thermoplastic elastomer) of 2/1 to 4/1.
- a mass ratio the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond/the thermoplastic elastomer
- thermoplastic elastomer refers to a macromolecular material which can be plasticized (fluidized) at a high temperature and processed like a plastic and exhibits properties of a rubber elastic body (elastomer) at normal temperature.
- thermoplastic elastomer is composed of a hard segment (plastic component) and a soft segment (elastic component) and has, for example, a block polymer-type structure in which a hard segment and a soft segment are chemically bound in a single polymer to form a block copolymer or a blend-type structure called "sea-island dispersion" or "polymer alloy", which is obtained by physically mixing a polymer constituting a hard segment and a polymer constituting a soft segment.
- a block polymer-type thermoplastic elastomer can be produced by block copolymerization.
- a blend-type thermoplastic elastomer composition after producing a soft segment and a hard segment, the thus obtained hard segment and soft segment are physically dispersed using a kneader such as a Banbury mixer or a biaxial extruder, thereby a blend-type thermoplastic elastomer composition can be obtained.
- the block copolymer is preferably a copolymer of ethylene and an ⁇ -olefin.
- the ⁇ -olefin include ⁇ -olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene and 1-octene. These ⁇ -olefins may be used individually, or two or more thereof may be used in combination.
- a segment originated from a monomer other than ethylene and ⁇ -olefin may also be incorporated.
- examples of such other monomer include non-conjugated dienes having 5 to 15 carbon atoms, such as dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene and 1,5-dicyclooctadiene; vinyl ester compounds such as vinyl acetate; ethylenically unsaturated carboxylic acid ester compounds such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate and butyl acrylate; and vinylnitrile compounds such as acrylonitrile and methacrylonitrile.
- These other monomers may be used individually, or two or more thereof may be used in combination. Alternatively, these other monomers may be (co-)polymerized as well.
- blend-type thermoplastic elastomer suitably used in the present invention include those which contain an olefin resin as a hard segment and an olefin-based copolymer elastomer as a soft segment.
- Examples of the above-described olefin resin contained as a hard segment include low-density polyethylenes, high-density polyethylenes, linear high-density polyethylenes, linear low-density polyethylenes, branched low-density polyethylenes, ethylene homopolymers, propylene homopolymers, and copolymers of ethylene and an ⁇ -olefin.
- Examples of the ⁇ -olefin include ⁇ -olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene.
- the above-described olefin resins may be used individually, or two or more thereof may be used in combination.
- an elastomer which is a copolymer of ethylene and an ⁇ -olefin is preferably used.
- ⁇ -olefin for example, an ⁇ -olefin having 3 to 10 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene or 1-octene, is usually used.
- the above-described may be used individually, or two or more thereof may be used in combination.
- the soft segment may also contain other elastomer along with the olefin-based copolymer elastomer, as long as it does not deteriorate the effects of the present invention.
- other elastomer for example, a styrene-based elastomer such as polybutadiene, hydrogenated polybutadiene or hydrogenated polyisoprene; a polyvinyl chloride-based elastomer; a polyester-based elastomer such as polyether; a polyurethane-based elastomer; a nylon-based elastomer; or an elastic polymer such as natural rubber can be used.
- the mass ratio of the hard segment and the soft segment can be set as appropriate in accordance with the desired purpose.
- the catalyst used in the production of the thermoplastic elastomer according to the present invention is not particularly restricted and any known polymerization catalyst can be employed.
- the polymerization catalyst exemplified in the above to be used in the polymerization of a monomer having an unsaturated bond may also be employed.
- the method exemplified in the above to be used for performing the polymerization reaction of a monomer having an ethylenically unsaturated bond can be employed.
- thermoplastic elastomer in addition to the olefin resin and olefin-based copolymer, other component(s) such as other resin, a rubber, a cross-linking agent, a cross-linking auxiliary, a compatibilizing agent, a lubricant, an antistatic agent, a softening agent and/or a foaming agent may be blended as well. It is preferred that the above-described other component(s) be blended prior to the step of melting the thermoplastic elastomer and the above-described polymer obtained by the monomer having an ethylenically unsaturated bond; however, the above-described other component(s) may also be blended simultaneously with the melting step.
- other component(s) such as other resin, a rubber, a cross-linking agent, a cross-linking auxiliary, a compatibilizing agent, a lubricant, an antistatic agent, a softening agent and/or a foaming agent may be blended as well. It is preferred that the
- Examples of the above-described other resin include ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer, polyamide, poly(4-methyl-1-pentene), styrene-isoprene-styrene block copolymer, styrene-ethylenebutene-styrene block copolymer, styrene-ethylenepropylene-styrene block copolymer and styrene-butadienestyrene block copolymer.
- EVA ethylene-vinyl acetate copolymer
- EVA ethylene-ethyl acrylate copolymer
- polyamide poly(4-methyl-1-pentene
- styrene-isoprene-styrene block copolymer styrene-ethylenebutene-styrene block copolymer
- the above-described rubber is not particularly restricted, and it may be, for example, an amorphous random elastic copolymer which contains an olefin-derived repeating unit in an amount of not less than 50% of the high-molecular-weight component in the rubber.
- Such elastic copolymer examples include copolymers that are obtained by copolymerizing a combination of two or more monomers selected from the group consisting of ethylene and ⁇ -olefins having 3 to 10 carbon atoms. Further, the elastic copolymer may also be one which is obtained by copolymerizing a combination of two or more monomers selected from the group consisting of ethylene and ⁇ -olefins having 3 to 10 carbon atoms with a conjugated diene monomer and/or a non-conjugated diene monomer.
- Examples of the above-described ⁇ -olefins having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene and 1-octene.
- conjugated diene examples include butadiene, isoprene and chloroprene.
- non-conjugated diene monomer examples include dicyclopentadiene, 1,4-hexadiene, 1,5-cyclooctadiene, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene.
- cross-linking agent examples include organic peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-di(t-butylperoxy)3,5,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(peroxybenzoyl)hexyne-3 and dicumyl peroxide.
- organic peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-di(t-butylperoxy)3,5,5
- the above-described organic peroxide is added in an amount of 0.005 to 2.0 parts by mass, preferably 0.01 to 0.6 parts by mass, with respect to 100 parts by mass of the thermoplastic elastomer.
- the amount is less than 0.005 parts by mass, the effect of crosslinking reaction is limited, while when the amount is greater than 2.0 parts by mass, it becomes difficult to control the reaction and such a large amount is thus economically disadvantageous.
- the organic peroxide may be mixed with a diluent to be used in the form of a liquid or powder substance.
- oils examples include oils, organic solvents and inorganic fillers (such as silica and talc).
- cross-linking auxiliary examples include those which are capable of increasing the crosslinking degree of a crosslinked-type thermoplastic elastomer and thus improving the physical properties of the resulting thermoplastic elastomer composition, and a cross-linking auxiliary which has a plurality of double bonds in the molecule is preferably used.
- cross-linking auxiliary examples include tetraethylthiuram disulfide (TETD), tetramethylthiuram disulfide (TMTD), N,N'-m-phenylenebismaleimide, toluylenebismaleimide, p-quinonedioxime, nitrobenzene, diphenylguanidine, divinylbenzene, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allylmethacrylate.
- TETD tetraethylthiuram disulfide
- TMTD tetramethylthiuram disulfide
- N,N'-m-phenylenebismaleimide toluylenebismaleimide
- p-quinonedioxime nitrobenzene
- diphenylguanidine divinylbenzene
- ethylene glycol dimethacrylate polyethylene glycol dimethacryl
- the above-described cross-linking auxiliary is added in an amount of preferably 0.01 to 4.0 parts by mass, more preferably 0.05 to 2.0 parts by mass, with respect to 100 parts by mass of the thermoplastic elastomer.
- amount is less than 0.01 parts by mass, the effect of the addition may not be easily attained, while an amount of greater than 4 parts by mass may be economically disadvantageous.
- the irradiation dose of the electron beam be 1 kGray to 100 kGray.
- the moldability of the thermoplastic elastomer may be poor when it is melted, while when the irradiation dose is 100 kGray or greater, the molecular chain may be broken and/or the resultant may become sticky.
- a compatibilizing agent in order to improve the interfacial adhesion between the polyolefin resin and crosslinked rubber, a compatibilizing agent may be added as well.
- the compatibilizing agent include silane coupling agents such as silane-modified olefin resins and silane-modified olefin-based rubbers; and adhesive resins (e.g., polystyrene-polybutadiene-polystyrene block copolymers, polyolefin-based grafts and comb-type grafts).
- Examples of the above-described lubricant include the same ones as those exemplified in the above.
- the above-described lubricant is added in an amount of preferably 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass, with respect to 100 parts by mass of the thermoplastic elastomer.
- the amount is less than 0.03 parts by mass, the desired lubricity may not be attained, while when the amount is greater than 2 parts by mass, the lubricant component may bleed out to the surface of the resulting molded article of the thermoplastic elastomer composition and/or cause deterioration in the physical properties thereof.
- the antistatic agent examples include the same ones as those exemplified in the above. Further, the antistatic agent is added in an amount of preferably 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass, with respect to 100 parts by mass of the thermoplastic elastomer. When the amount of the antistatic agent is excessively small, the antistatic effect is insufficient, while when the amount is excessively large, the antistatic agent may bleed out to the surface and/or cause deterioration in the physical properties of the thermoplastic elastomer composition.
- softening agent examples include process oils and aliphatic cyclic saturated hydrocarbon resins.
- foaming agent examples include volatile foaming agents composed of a lower aliphatic hydrocarbon such as propane, butane or pentane, a lower alicyclic hydrocarbon such as cyclobutane or cyclopentane, and a halogenated hydrocarbon such as monochlorodifluoromethane, dichlorodifluoromethane, trichlorodifluoroethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, methyl chloride, ethyl chloride or methylene chloride; gaseous foaming agents such as nitrogen, carbon dioxide gas, oxygen and air; pyrolytic foaming agents composed of sodium bicarbonate, ammonium bicarbonate, dinitrosopentamethylenetetramine, toluenesulfonyl hydrazide, azodicarbonamide, p,p'-oxybisbenzenesulfonylhydrazide,
- the amount of the foaming agent to be used is appropriately selected as required.
- thermoplastic elastomer and foaming agent are carried out inside an extruder or the like by kneading them while melting the thermoplastic elastomer; however, in cases where a pyrolytic foaming agent is used, it may be mixed with the thermoplastic elastomer in advance before feeding the thermoplastic elastomer to an extruder or the like. Alternatively, the pyrolytic foaming agent may be fed to an extruder or the like separately from the thermoplastic elastomer.
- the foaming agent may be injected into molten thermoplastic elastomer from the middle section of a screw of a vent-type extruder or the like.
- thermoplastic elastomer In cases where a foaming agent is used in the thermoplastic elastomer, the thermoplastic elastomer and the foaming agent are extrusion-foamed via a die installed at the tip of an extruder.
- the shape of the resulting foamed article is arbitrary and it is not particularly restricted; however, the foamed article may be in the form of, for example, a film, a sheet, a pipe or a cylinder.
- additives may also be blended.
- the additives may be added at the time of polymerizing the monomer having an ethylenically unsaturated bond or polymerizing the thermoplastic elastomer, as long as the additives do not inhibit the polymerization.
- other additives may be blended and uniformly dispersed in an amount appropriate for the intended purpose at the time of melt-kneading the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- thermoplastic elastomer composition be prepared by kneading or stirring until a uniform composition is attained using a biaxial extruder equipped with a heating device, a Banbury mixer, a pressure kneader, a Henschel mixer, a Brabender kneader, disperser or the like.
- additives examples include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, ultraviolet absorbers, hindered amine compounds, heavy metal inactivators, nucleating agents, flame retardants, metallic soaps, hydrotalcites, fillers, lubricants, antistatic agents, pigments, dyes and plasticizers.
- phenolic antioxidants examples include the same ones as those exemplified in the above and phenolic antioxidants represented by the above-described Formula (1); however, tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane is particularly preferably used since it is relatively inexpensive and has good cost performance.
- the phenolic antioxidant used as the above-described other additive is added in an amount of preferably 0.001 to 0.5 parts by mass, particularly preferably 0.01 to 0.3 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- Examples of the above-described phosphorus-based antioxidants include the same ones as those compounds exemplified in the above as the phosphorus-based antioxidant to be added.
- the above-described phosphorus-based antioxidant is used in an amount of preferably 0.01 to 0.3 parts by mass with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- sulfur-based antioxidants examples include the same ones as those exemplified in the above for the thioester-based antioxidant to be added.
- the sulfur-based antioxidant is used in an amount of preferably 0.01 to 0.3 parts by mass with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- Examples of the above-described ultraviolet absorbers include the same ones as those exemplified in the above.
- the ultraviolet absorber is used in an amount of 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- hindered amine-based light stabilizers examples include the same ones as those exemplified in the above.
- the hindered amine-based light stabilizer is used in an amount of 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- nucleating agents examples include the same ones as those exemplified in the above.
- the nucleating agent is used in an amount of 0.001 to 10 parts by mass, more preferably 0.005 to 5 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- Examples of the above-described flame retardants include the same ones as those exemplified in the above.
- the flame retardant is used in an amount of 1 to 70 parts by mass, more preferably 10 to 30 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- Examples of the above-described fillers include the same ones as those exemplified in the above.
- Examples of the above-described lubricants include the same ones as those exemplified in the above.
- antistatic agents examples include the same ones as those exemplified in the above.
- the polymer obtained by the present invention there is not particular restriction, and the polymer can be molded by a known molding method such as extrusion molding, injection molding, hollow molding, blow molding or compression molding.
- the coated member obtained by the present invention can be used in the form of, for example, but not limited to, a film, a sheet, a cylinder, a box or a sphere.
- Specific examples of the use of the coated member include automobile exterior parts where the outer appearance of the paint surface is given high importance, such as a bumper, a spoiler, a side guard molding or a radiator grill.
- a test piece of 15 mm in width and 100 mm in length was prepared. After manually abrasing the thus obtained test piece over a length of 50 mm in the longitudinal direction, both ends of the resulting test piece was pinched and detached in the 180-degree direction using a tensile tester (STROGRAPH APII, manufactured by Toyo Seiki Seisaku-sho, Ltd.) at a tensile rate of 300 mm/min to measure the maximum strength as adhesion strength.
- a tensile tester (STROGRAPH APII, manufactured by Toyo Seiki Seisaku-sho, Ltd.) at a tensile rate of 300 mm/min to measure the maximum strength as adhesion strength.
- a packaging bag of 130 mm ⁇ 170 mm was prepared and, as a content, 200 ml of water was enclosed in the packaging bag.
- the packaging bag was then subjected to a hot water-stationary retort sterilization treatment at 120°C for 30 minutes. After the sterilization treatment, the packaging bag was cooled to room temperature and its content, water, was mixed with chloroform to be extracted into chloroform, followed by concentration. Thereafter, using a gas chromatograph-mass spectrometer, low-molecular weight substances, such as the blended additives and their oxides and decomposed matters, were quantified to determine the eluted amount of each blended additives. The ratio of the eluted amount of each additive with respect to the blended amount was calculated to determine the ratio of elution.
- test pieces of 40 mm in width and 100 mm in length were prepared and laminated such that the tip of one of the test pieces in the longitudinal direction overlaps with the tip of the other test piece in the longitudinal direction by 15 mm. Then, the thus laminated test pieces were heat-sealed at 200°C and 1 kg/cm 2 for 1 second. Using a tensile tester, the thus heat-sealed test pieces were detached in the 180-degree direction at a tensile rate of 300 mm/min to measure the tensile strength as heat-seal strength.
- the resulting homogeneous solution was cooled to room temperature and the entire amount thereof was then dropwisely charged to 200 ml (1.8 mol) of titanium tetrachloride, which had been kept at -20°C, over a period of 1 hour. Thereafter, the resultant was heated to 110°C over a period of 4 hours and once the temperature reached 110°C, 2.68 ml (12.5 mmol) of diisobutyl phthalate was added and the resulting mixture was allowed to react for 2 hours with stirring while maintaining the temperature at 110°C. After completion of the reaction, the resulting solids were recovered by hot filtration and suspended in 200 ml of titanium tetrachloride, and the suspension was allowed to react with heating at 110°C for 2 hours. Thereafter, the resulting solids were recovered again by hot filtration and thoroughly washed with 110°C decane and hexane until no free titanium compound was detected in the washings, thereby obtaining a solid Ti catalyst component.
- the solid Ti catalyst component obtained by the above-described method was stored in the form of a heptane slurry with an addition of heptane to a concentration of 5 mg/mL.
- the solid Ti catalyst component was determined to have the following composition: 2.9% by mass of titanium, 56.0% by mass of chlorine, 17.0% by mass of magnesium and 20.9% by mass of isobutyl phthalate.
- the atmosphere inside the autoclave was pressurized with propylene at 5 kgf/ cm 2 G to perform polymerization reaction at 80°C for 2 hours.
- the solvent was removed under reduced pressure at 50°C and the resulting polymer was dried in vacuum at 40°C for 5 hours to obtain a polyethylene powder.
- an anchor coating agent manufactured by TOYOBO Co., Ltd.; trade name: TOYOBO ESTER FILM E5100
- a laminate film was produced in the same manner as in the above-described Example 1-1, except that the extrusion temperature by T-die was changed as shown in Table 2, that the supporting substrate was changed to an ester film (manufactured by TOYOBO Co., Ltd.; trade name: TOYOBO ESTER FILM T4100), that the anchor coating agent was not used, and that an air having an ozone concentration of 12.9 g/m 3 was blown against a surface of the film sheet extruded from the T-die, which surface was press-adhered to the supporting substrate, in an amount of 3 Nm 3 per hour.
- the extrusion temperature by T-die was changed as shown in Table 2, that the supporting substrate was changed to an ester film (manufactured by TOYOBO Co., Ltd.; trade name: TOYOBO ESTER FILM T4100), that the anchor coating agent was not used, and that an air having an ozone concentration of 12.9 g/m 3 was blown against a surface of the film
- a laminate film was produced in the same manner as in the above-described Example 1-1 (production of laminate film), except that the anchor coating agent was changed to an adhesive for dry lamination (manufactured by Takeda Pharmaceutical Company Limited trade name: A-515/A-50) and that the extrusion temperature by the T-die was changed from 250°C to 280°C.
- the laminate film according to the present invention has excellent resistance to its content, particularly a liquid matter; therefore, the laminate film according to the present invention can be suitably used as a safer and more hygienic packaging material for food articles, pharmaceutical products and the like.
- the thus obtained homogeneous solution was cooled to room temperature and the entire amount thereof was then dropwisely charged to 200 ml (1.8 mol) of titanium tetrachloride, which had been kept at -20°C, over a period of 1 hour. Thereafter, the resultant was heated to 110°C over a period of 4 hours and once the temperature reached 110°C, 2.68 ml (12.5 mmol) of diisobutyl phthalate was added and the resulting mixture was maintained at this temperature for 2 hours under stirring. After completion of the 2-hour reaction, the resulting solids were recovered by hot filtration and resuspended in 200 ml of titanium tetrachloride.
- the solid Ti catalyst component synthesized by the above-described production method was stored in the form of a heptane slurry and a portion thereof was taken out and dried and the catalyst composition was analyzed.
- the solid Ti catalyst component obtained in this manner was determined to have the following composition: 3.1 % by weight of titanium, 56.0% by weight of chlorine, 17.0% by weight of magnesium and 20.9% by weight of isobutyl phthalate.
- the amounts of the blended stabilizer shown in Table 4 are each an amount (parts by mass) with respect to a total of 100 parts by mass of the polymer obtained from the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer. Further, the amounts of the blended antioxidant shown in Table 4 are each an amount of the antioxidant by itself prior to being masked.
- the amount of the blended stabilizer in the whole resin composition is a total of the amount added at the time of polymerizing a monomer having an ethylenically unsaturated bond to produce a polymer and the amount at the time of polymerizing to produce a thermoplastic elastomer. This also applies to the following Production Examples in the same manner.
- Polypropylene powder B was obtained in the same manner as in the above-described Production Example 1, except that neither the phenoxide solution nor the phosphite solution was added.
- thermoplastic elastomer A was obtained.
- This alumina in an amount of 7 g was suspended in 50 mL of n-hexane and 82 mg (1.4 mmol in terms of aluminum unit) of methylaluminoxane dissolved in 10 mL of toluene was added to the resulting suspension. After stirring the thus obtained mixture at room temperature for 30 minutes, 9 mL of 0.16M solution of tetrabenzylzirconium dissolved in toluene was added, and the resultant was stirred at room temperature for another 30 minutes. Neither zirconium nor aluminum was detected in the liquid phase.
- the solid catalyst prepared in this manner was found to contain 0.2 mmol/g of zirconium and 0.2 mmol/g of aluminum.
- thermoplastic elastomer B was obtained in the same manner as in the above-described Production Example 3, except that no phenoxide solution was added.
- the thus obtained pellet was injection-molded using a laboratory micro-injection molding machine (manufactured by DSM Xplore; Compounder 15, Injection molder 12) at an injection temperature of 220°C and a die temperature of 50°C, thereby preparing a tabular test piece of 50 mm ⁇ 90 mm ⁇ 2 mm. After the injection molding, the thus obtained test piece was left to stand for 48 hours in a 23°C incubator and then subjected to the following measurements. The results thereof were evaluated by the following procedures.
- test piece was exposed to a saturated vapor of 1,1,1-trichloroethane for 30 seconds and the surface was washed. Then, the resulting test piece was dried for 10 minutes in an oven whose temperature was set at 90°C and subsequently subjected to a plasma treatment using a microwave plasma treatment apparatus (BH-10, manufactured by NISSIN Inc.).
- BH-10 microwave plasma treatment apparatus
- the test piece was painted with acryl-melamine-type pearl mica in accordance with the following procedures (1) to (7).
- the painting was performed by using R320, R331 and R341 (trade names; manufactured by Nippon Bee Chemical Co., Ltd.), with R320 (trade name; manufactured by Nippon Bee Chemical Co., Ltd.) being a color base, R331 (trade name; manufactured by Nippon Bee Chemical Co., Ltd.) being a mica base and R341 (trade name; manufactured by Nippon Bee Chemical Co., Ltd.) being a clear paint.
- test piece thus painted with the acryl-melamine-type pearl mica by the above-described procedures was immersed in 40°C water for 240 hours. Then, using a cutter knife, incisions were made on the paint coating film in a grid form to separate it into 100 1-mm square sections, and a cellophane tape was pasted thereon. The cellophane tape was removed and the number of sections that were not removed by the cellophane tape was measured to evaluate the adhesion of the coating film.
- the above-described test piece painted with the acryl-melamine-type pearl mica was left to stand in a 90°C incubator for 240 hours. Then, the change in the yellowness of the coating film before and after heating ( ⁇ b) was measured to evaluate the heat-yellowing resistance. The measurement was performed by using a spectrocolorimeter (model: T-4, manufactured by Suga Test Instruments Co., Ltd.).
- reaction vessel To a pressure-resistant reaction vessel, 215 ml of 95% ethanol aqueous solution was loaded as an extraction solvent. The reaction vessel was hermetically sealed and left to stand for 1 day in a 121°C incubator and a 49°C incubator. After confirming that the temperature of the extraction solvent had reached 121°C, three of the above-described test pieces, which were skewered with a glass rod, were immersed in the extraction solvent in such a manner that the test pieces did not float. Then, the reaction vessel was returned to the 121°C incubator and left to stand therein for 2 hours.
- test pieces were taken out and the surfaces thereof were washed with fresh extraction solvent. Then, the three test pieces were again skewered with a glass rod and immersed in the extraction solvent in the pressure-resistant reaction vessel which had been left to stand in the 49°C incubator. The reaction vessel was hermetically sealed, returned to the 49°C incubator and left to stand therein for 10 days. After the 10-day incubation, the test pieces were taken out and the surfaces thereof were washed with fresh extraction solvent.
- the extraction solvents used in the 121°C and 49°C incubators and the extraction solvents used in the washing operations were recovered and concentrated under reduced pressure using a rotary evaporator.
- the amount of the stabilizer composition extracted in each of the thus concentrated extraction solvents was quantitatively analyzed by the following method.
- Example 4-1 Example 4-2
- Example 4-3 Example 4-4 Additive formulation Composition of polypropylene powder Polypropylene powder A 67 67 80 80
- Ratio of elution represents the ratio of the amount of the eluted antioxidant in the respective formulations, taking the amount of the eluted antioxidant in Comparative Example 4-4 as 1.
- Example 4-1 the coated member of the present invention showed good adhesion with a coating film and good heat-yellowing resistance and had only a small amount of elution. From the results of Example 4-2, it was confirmed that the heat resistance can be further improved by further addition of a phosphorus-based antioxidant.
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Abstract
(A) adding, before or during said polymerization of said monomer having an ethylenically unsaturated bond, a phenolic antioxidant represented by the following Formula (1), that is masked with an organoaluminum compound, to at least one of a catalyst system, a polymerization system and a piping, and performing said polymerization such that said phenolic antioxidant is incorporated in an amount of 0.001 to 0.5 parts by mass with respect to a total of 100 parts by mass of said polymer obtained by said polymerization of said monomer having an ethylenically unsaturated bond and said thermoplastic elastomer; and
(B) melt-kneading said polymer obtained by said polymerization of said monomer having an ethylenically unsaturated bond with said thermoplastic elastomer:
(C) molding the composition from step B into an article.
Description
- The present invention relates to a method of producing a laminate film. More particularly, the present invention relates to a method of producing a laminate film which can yield a laminate film having excellent adhesion with a laminate base material and reduce the amount of an anchor coating agent or an adhesive for dry lamination to be used.
- Further, the present invention also relates to a method of producing a resin composition for a coated member which comprises a polymer obtained by polymerization of a monomer having an ethylenically unsaturated bond and a thermoplastic elastomer. More particularly, the present invention relates to a method of producing a resin composition for a coated member, by which a resin composition for a coated member, which shows excellent adhesion with a coating film after a plasma treatment and can have suppressed yellowing, can be produced.
- As the use of a laminate film, packaging materials utilizing a film made of a thermoplastic resin have been conventionally proposed, and there are known laminate films in which an olefin resin film is laminated on a laminate base material of polyester, polyamide, metallic foil or the like by press-adhesion with heating (heat sealing) or application of an adhesive. Among olefin resins, in particular, polyethylene is widely used in the food packaging material applications since it is inexpensive and easily processable and exhibits excellent blocking of water vapor.
- However, an olefin resin itself is inert and has poor adhesive force; therefore, for example, in Patent Document 1, a method of producing a laminate film by subjecting the surface of a laminate base material to an anchor coating treatment with an anchoring agent such as a polyurethane or an isocyanate compound and then laminating an ozone-treated olefin resin thereon is proposed.
- There have been also proposed several methods of producing a laminate film without using an anchor coating agent and, for example, in Patent Document 2, a method of improving the adhesion of a film by subjecting the film to an ozone treatment under a specific condition is disclosed.
- By the way, olefin resins have poor stability against heat and light and are thus easily oxidized/degraded when exposed to a high-temperature environment or a strong light, so that the service life required as a plastic product cannot be attained. In order to prevent such oxidation/degradation, a stabilizer such as a phenolic antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a hydroxylamine compound, a hindered amine compound, an ultraviolet absorber or an acid scavenger is commonly added. In particular, a phenolic antioxidant is widely utilized because of its high thermostability effect in high-temperature processing.
- Examples of a method of adding a stabilizer to an olefin resin include a method in which an olefin resin obtained by polymerization of an olefin monomer and is mixed with a stabilizer and the resulting mixture is melt-kneaded using a processing equipment such as an extruder to disperse the stabilizer in the olefin resin; and a method in which a stabilizer is added before or during polymerization of an olefin monomer. Such a method of blending an olefin resin and a stabilizer by melt-kneading has a problem in that the stabilizer must be added in an amount more than necessary in order to mitigate the defective dispersion of the stabilizer in the olefin resin.
- As a method of adding a stabilizer before or during polymerization of an olefin monomer, for example, Patent Document 3 discloses a production method in which an α-olefin is polymerized in the presence of a phosphorus-based antioxidant. It is shown that a polymer obtained by polymerizing an α-olefin in the presence of a phosphorus-based antioxidant can attain superior stabilization effect as compared to a case where a phosphorus-based antioxidant is not used at the time of performing polymerization but is added to a polymer obtained by polymerization of an α-olefin.
- Further, in Patent Document 4, it is shown that, by using a specific phosphorus-based antioxidant at the time of polymerizing an olefin, the polymerization is not inhibited and a polymer in which coloration caused by contact with water is suppressed can be obtained.
- Meanwhile, in cases where a phenolic antioxidant-containing stabilizer is added before the polymerization of an olefin monomer, since phenol reduces the catalytic activity of an olefin polymerization catalyst, there are problems that the resulting olefin resin is colored and a desired polymerization cannot be achieved.
- Further, while a phenolic antioxidant can provide high thermostability in high-temperature processing of an olefin resin, when a molded article of an olefin resin is immersed in water or a solvent such as alcohol, there are cases where the blended phenolic antioxidant elutes out of the molded article.
- As a polymerization method in which a phenolic antioxidant is prevented from reducing the catalytic activity of a polymerization catalyst, for example, in Patent Documents 5 and 6, it is shown that inhibition of a polymerization catalyst can be suppressed by adding a phenolic antioxidant masked with an organoaluminum compound before or during polymerization of a monomer having an ethylenically unsaturated bond.
- Moreover, an olefin resin obtained by polymerization of a monomer having an ethylenically unsaturated bond is inexpensive, has a low specific gravity and a high rigidity, exhibits good moldability and thus can be molded into a large molded article; therefore, such an olefin resin has been increasingly utilized in a variety of applications. In automobile applications, the use of such an olefin resin has been expanding to structural members and the like, examples of which include exterior parts such as bumpers; interior parts such as instrument panels and trims; engine room interior components such as fan casings; and a variety of module materials.
- In general, such resin compositions used in automobile interior and exterior parts such as bumpers are produced by blending, as required, for example, an olefin resin, an elastomer, an inorganic filler, a pigment such as carbon black, a light stabilizer, an ultraviolet absorber, a hindered phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and a lactone-based antioxidant.
- Conventionally, bumpers are generally provided as unpainted or completely painted products; however, in recent years, in accordance with design requirements, bumpers have been widely provided in a partially unpainted condition. Therefore, it is demanded not only that a resin composition for a bumper have good weathering resistance and good adhesion with a coating film, but also that the bumper and its coating film be not discolored even when exposed to heat, sunlight and the like.
- In general, in order to improve the weathering resistance and photostability of a molded article of an olefin resin, a variety of additives such as an antioxidant, a hindered amine-based light stabilizer and an ultraviolet absorber are blended; however, there is a problem in that such additives blended in an olefin resin are strongly affected by heat and sunlight and diffuse, migrate or bleed out from the resin to a coating film, thereby causing yellowing of the coating film. In particular, it is known that a phenolic antioxidant is converted into quinoline after bleeding out and causes yellowing of a coating film.
- In order to inhibit the above-described yellowing of a coating film, for example, a method of preventing diffusion, migration and bleeding-out of additives by overcoating the coating film with an acryl-melamine system, a two-component urethane system, a polyester-melamine system, a polyester-urethane system or the like can be employed; however, even after the overcoating, a coating color of a high brightness (L value of 60 or higher) may cause yellowing of the coating film under natural environment. Further, by this method, a partially unpainted bumper cannot be obtained.
- Meanwhile, Patent Documents 7 and 8 propose methods of inhibiting yellowing of a painted bumper with specific amounts and types of an antioxidant and a light stabilizer.
- In addition, Patent Document 9 proposes a method in which specific four types of antioxidants and, as required, a benzoate-based light stabilizer and a hindered amine-based light stabilizer are blended into a polypropylene resin composition which contains a specific propylene-ethylene block copolymer, elastomer and inorganic filler.
- Patent Documents 6, 10 and 11 describe methods in which a phenolic antioxidant masked with an organoaluminum compound is added before or during polymerization of a monomer having an ethylenically unsaturated bond.
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- Patent Document 1: Japanese Unexamined Patent Application Publication No.
S61-283533 - Patent Document 2: Japanese Unexamined Patent Application Publication No.
S63-49423 - Patent Document 3: Japanese Unexamined Patent Application Publication No.
S63-92613 - Patent Document 4: Japanese Unexamined Patent Application Publication No.
H8-208731 - Patent Document 5: Japanese Unexamined Patent Application Publication No.
2006-52241 - Patent Document 6: Japanese Unexamined Patent Application Publication No.
2006-282985 - Patent Document 7: Japanese Unexamined Patent Application Publication No.
H6-107897 - Patent Document 8: Japanese Unexamined Patent Application Publication No.
H7-179719 - Patent Document 9: Japanese Unexamined Patent Application Publication No.
2003-29270 - Patent Document 10: Japanese Unexamined Patent Application Publication No.
2005-206625 - Patent Document 11: Japanese Unexamined Patent Application Publication No.
2005-255953 - However, some of the anchor coating agents used in an anchor coating treatment contain, as a diluent, an organic solvent such as ethyl acetate, toluene or methyl ethyl ketone and such anchor coating agents have problems relating to deterioration of work environment due to vaporization of the solvent and disaster prevention, as well as a problem that, if the adhesive is not sufficiently dried, the organic solvent remains in the laminate film and gives odor to its contents.
- In addition, in cases where, as a content, a liquid containing a component such as water, edible oil or alcohol is filled and packaged by a laminate film, there has been indicated a problem that elution or the like of an anchor coating agent component caused by the permeability of the liquid reduces the interlayer adhesion strength of the laminate film and detachment thus occurs between the film layers.
- Furthermore, the method according to Patent Document 2 has a problem that, due to the high melt-extrusion temperature, the resin and the blended additives are degraded to cause odor in the contents.
- Meanwhile, in Patent Documents 5 and 6, the application of the methods to a laminate film is not examined and neither the adhesive property of a laminate film nor the elution of the additives after film formation is examined at all.
- In view of the above, an object of the present invention is to provide a method of producing a laminate film by which a laminate film having excellent adhesion with a laminate base material, in which laminate film the amount of elution of an additive into a solvent is small, can be produced.
- Further, there is still a room for improvement with regard to the problem of coloration of a coated member. Moreover, in cases where a molded article is subjected to a plasma treatment and then coated, in the above-described methods of Patent Documents 7 to 9, there is a problem that the additive(s) blended after the plasma treatment elute out to the surface of the resulting molded article and the adhesion of the coating film is thereby impaired.
- Therefore, another object of the present invention is to provide a method of producing a resin composition for a coated member, by which a resin composition for a coated member which shows good secondary adhesion with a coating film and good heat-yellowing resistance can be obtained.
- In view of the above-described current circumstances, the present inventors intensively studied to discover that the above-described problems can be solved by using a polyolefin stabilized by an addition of a specific phenolic antioxidant before or during polymerization of an ethylenically unsaturated monomer, thereby completing the present invention.
- In addition, the present inventors also discovered that the above-described problems can be solved by adding a specific stabilizer before or during polymerization of a monomer having an ethylenically unsaturated bond, thereby completing the present invention.
- Due to the recent advancements in the polymerization technologies, it is now possible to obtain a stabilized polymer by performing polymerization with an addition of a stabilizer composition to a polymerization catalyst, a polymerization apparatus or a piping thereof. This method can omit the step of blending a stabilizer composition by post-polymerization melt-kneading and allows the stabilizer to be uniformly dispersed in the resulting polymer; therefore, the amount of the stabilizer to be blended can be consequently reduced. However, since a phenol compound adversely affects the polymerization catalyst to impair the polymerization, a stabilizer composition containing a phenolic antioxidant could not be added in the polymerization step.
- The present inventors have proposed methods in which, by using a phenolic antioxidant masked with an organoaluminum compound, even when the phenolic antioxidant is added before or during polymerization of a monomer having an ethylenically unsaturated bond, the resulting polymer is stabilized without impairing the activity of a polymerization catalyst even when the phenolic antioxidant is added before or during the polymerization (Patent Documents 6, 10 and 11).
- When the present inventors, based on these findings, added a specific phenolic antioxidant masked with an organoaluminum compound before or during polymerization of a monomer having an ethylenically unsaturated bond, it was revealed that the resulting resin composition had good adhesion with a coating film and good heat-yellowing resistance.
- That is, the method of producing a laminate film according to the present invention is characterized by comprising the step of adding, before or during polymerization of a monomer having an ethylenically unsaturated bond, a phenolic antioxidant represented by the following Formula (1), which is masked with an organoaluminum compound, to at least one of a catalyst system, a polymerization system and a piping, such that the phenolic antioxidant is incorporated in an amount of 0.001 to 0.5 parts by mass with respect to 100 parts by mass of a polymer obtained by the polymerization:
- Further, it is preferred that the method of producing a laminate film according to the present invention further comprise the step of adding, before or during the polymerization of a monomer having an ethylenically unsaturated bond, a phosphorus-based antioxidant to at least one of the catalyst system, the polymerization system and the piping in an amount of 0.001 to 3 parts by mass with respect to 100 parts by mass of the polymer obtained by the polymerization.
- Still further, in the method of producing a laminate film according to the present invention, it is preferred that the above-described organoaluminum compound be a trialkylaluminum.
- The laminate film according to the present invention is characterized by being produced by the method of producing a laminate film.
- The method of producing a resin composition for a coated member according to the present invention is a method of producing a resin composition for a coated member, which resin composition comprises a polymer obtained by polymerization of a monomer having an ethylenically unsaturated bond and a thermoplastic elastomer, the method being characterized by comprising the steps of:
- (A) adding, before or during the polymerization of the monomer having an ethylenically unsaturated bond, a phenolic antioxidant represented by the following Formula (1), which is masked with an organoaluminum compound, to at least one of a catalyst system, a polymerization system and a piping, such that the above-described phenolic antioxidant is incorporated in an amount of 0.001 to 0.5 parts by mass with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer; and
- (B) melt-kneading the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond with the thermoplastic elastomer:
- In the above-described step (B) of the method of producing a resin composition for a coated member according to the present invention, it is preferred that the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer be melt-kneaded at a mass ratio, the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond/the thermoplastic elastomer, of 2/1 to 4/1.
- Further, in the method of producing a resin composition for a coated member according to the present invention, it is preferred that the above-described thermoplastic elastomer be obtained by polymerization of a monomer having an ethylenically unsaturated bond, before or during which polymerization of the monomer having an ethylenically unsaturated bond a phenolic antioxidant represented by the above-described Formula (1), which is masked with an organoaluminum compound, is added to at least one of a catalyst system, a polymerization system and a piping.
- Still further, it is preferred that the method of producing a resin composition for a coated member according to the present invention further comprise the step of adding, before or during the polymerization of the monomer having an ethylenically unsaturated bond, a phosphorus-based antioxidant to at least one of the catalyst system, the polymerization system and the piping, such that the phosphorus-based antioxidant is incorporated in an amount of 0.001 to 3 parts by mass with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- Yet still further, in the method of producing a resin composition for a coated member according to the present invention, it is preferred that the above-described organoaluminum compound be a trialkylaluminum.
- The method of producing a coated member according to the present invention is characterized by comprising the step of coating a molded article of a resin composition obtained by the above-described method of producing a resin composition for a coated member. It is preferred that the method of producing a coated member according to the present invention also comprise the step of subjecting the above-described molded article of the resin composition to a plasma treatment before the above-described coating step.
- The coated member according to the present invention is characterized by being produced by the above-described method of producing a coated member and it is preferred that the coated member contain a light stabilizer and a filler.
- By the present invention, a method of producing a laminate film, by which a laminate film having excellent adhesion with a laminate base material can be obtained, in which laminate film the amount of elution of an additive into a solvent is small and the amount of an anchoring agent used is reduced, which laminate film can also be utilized in food articles and sanitary goods such as medical supplies, can be provided.
- Further, by the present invention, a method of producing a resin composition for a coated member, by which a resin composition for a coated member which shows good secondary adhesion with a coating film and good heat-yellowing resistance can be obtained, can be provided.
- The phenolic antioxidant used in the method of producing a laminate film according to the present invention is a compound represented by the following Formula (1):
- Examples of the alkyl group having 1 to 5 carbon atoms which is optionally branched and represented by R1 and R2 in the above-described Formula (1) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, sec-pentyl group and tert-pentyl group; however, the alkyl group is particularly preferably a tert-butyl group since it has good effect of stabilizing the phenolic antioxidant.
- Examples of the arylalkyl group having 7 to 9 carbon atoms which is represented by R1 and R2 in the above-described Formula (1) include benzyl and 1-methyl-1-phenylethyl.
- Examples of the alkyl group having 1 to 30 carbon atoms which is optionally branched and represented by R in the above-described Formula (1) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, isobutyl group, pentyl group, isopentyl group, t-pentyl group, hexyl group, heptyl group, n-octyl group, isooctyl group, t-octyl group, nonyl group, isononyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group; however, in the present invention, an alkyl group having 12 to 24 carbon atoms is particularly preferred. When the alkyl group has less than 12 carbon atoms, the phenolic antioxidant may be easily vaporized, while when the alkyl group has more than 24 carbon atoms, the ratio of phenol relative to the molecular weight of the phenolic antioxidant is decreased, so that the stabilizing effect may be reduced.
- These alkyl groups are also optionally interrupted by an oxygen atom, a sulfur atom or the below-described aryl group, and the hydrogen atoms of the alkyl groups are also optionally substituted with a hydroxy group, a cyano group, an alkenyl group, a chain aliphatic group such as an alkenyloxy group, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, isoxazole, isothiazole, pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, morpholine, 2H-pyran, 4H-pyran, phenyl, biphenyl, triphenyl, naphthalene, anthracene, pyrrolidine, pyrindine, indolizine, indole, isoindole, indazole, purine, quinolizine, quinoline, isoquinoline or a cyclic aliphatic group such as a cycloalkyl group. In addition, these interruptions or substitutions may also exist in combination.
- The alkenyl group having 2 to 30 carbon atoms which is optionally branched and may be represented by the above-described R is the above-described alkyl group into which a carbon-carbon double bond is introduced. In the same manner as in the case of the above-described alkyl group, an alkenyl group having 12 to 24 carbon atoms is particularly preferred.
- Examples of the cycloalkyl group having 3 to 12 carbon atoms which is optionally substituted and represented by R in the above-described Formula (1) include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group and cyclodecyl group. The hydrogen atoms of the cycloalkyl group are optionally substituted with an alkyl group, an alkenyl group, an alkenyloxy group, a hydroxy group or a cyano group, and the alkyl group is also optionally interrupted by an oxygen atom or a sulfur atom.
- Examples of the aryl group having 6 to 18 carbon atoms which is optionally substituted and represented by R in the above-described Formula (1) include phenyl group, methylphenyl group, butylphenyl group, octylphenyl group, 4-hydroxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-t-butylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, phenanthryl group, benzyl group, phenylethyl group and 1-phenyl-1-methylethyl group. Further, the hydrogen atoms of the aryl group are optionally substituted with an alkyl group, an alkenyl group, an alkenyloxy group, a hydroxy group or a cyano group, and the alkyl group is also optionally interrupted by an oxygen atom or a sulfur atom.
-
- In cases where the phenolic antioxidant represented by the above-described Formula (1) which is masked with an organoaluminum compound is added, the phenolic antioxidant is added in an amount of 0.001 to 0.5 parts by mass, preferably 0.001 to 0.3 parts by mass, with respect to 100 parts by mass of the polymer obtained by the polymerization. When the amount of the phenolic antioxidant is less than 0.001 parts by mass, the effect of the addition may not be attained. Meanwhile, the phenolic antioxidant can be added in an amount of greater than 0.5 parts by mass; however, such an amount is economically disadvantageous because it causes the resulting polymer to be colored and the effect of the addition is limited.
- As for a method of adding the phenolic antioxidant represented by the above-described Formula (1) which is masked with an organoaluminum compound, there is no particular restriction. Examples of suitable mode thereof include one in which the masked phenolic antioxidant is added and mixed in at least one of a catalyst feed tank, a polymerization apparatus and a piping of the production line.
- The above-described masking can be performed by mixing and stirring an organoaluminum compound and the phenolic antioxidant in an inert solvent. By the mixing and stirring, the hydrogen of the phenolic hydroxyl group of the phenolic antioxidant is substituted with the organoaluminum compound. The above-described phenolic antioxidant and organoaluminum compound may be mixed with stirring prior to being added to at least one of the catalyst system, the polymerization system and the piping. Alternatively, the phenolic antioxidant and the organoaluminum compound may be added and mixed separately in at least one of the catalyst system, the polymerization system and the piping.
- In cases where a compound produced as a by-product in the masking reaction of the phenolic antioxidant does not affect the polymerization reaction of the monomer or the resulting polymer, the masked phenolic antioxidant may be used as is; however, in cases where the by-produced compound inhibits the polymerization, it is preferred to remove the compound by vacuum distillation or the like before adding the masked phenolic antioxidant to at least one of the catalyst system, the polymerization system and the piping.
- It is desired that the above-described masked phenolic antioxidant be capable of regenerating phenol by undergoing a reaction with a hydrogen-donating compound such as water, an alcohol or an acid, which is added as a deactivation treatment of the polymerization catalyst after the polymerization.
- Examples of the above-described organoaluminum compound include alkylaluminums and alkylaluminum hydrides, and the organoaluminum compound is preferably an alkylaluminum, particularly preferably a trialkylaluminum. Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum, and these compounds may be used individually or in combination as a mixture. In addition, an aluminoxane obtained by a reaction between an alkylaluminum or an alkylaluminum hydride and water can also be used in the same manner.
- It is desired that the mixing ratio of the organoaluminum compound and the phenolic antioxidant represented by the above-described Formula (1) (the organoaluminum compound/the phenolic antioxidant represented by the above-described Formula (1)) be, in terms of mass ratio, 1/5 to 100/1. When the ratio of the organoaluminum compound is lower than 1/5, the excessive amount of the phenolic antioxidant may adversely affect the catalyst activity, while when the ratio is higher than 100/1, an aluminum compound remains in the resulting polymer after the polymerization and this may cause deterioration in the physical properties of the polymer or affect the component ratio of the catalyst metal, making it unable to perform the desired polymerization.
- Examples of the above-described inert solvent include aliphatic and aromatic hydrocarbon compounds. Examples of the aliphatic hydrocarbon compounds include saturated hydrocarbon compounds such as n-pentane, n-hexane, n-heptane, n-octane, isooctane and refined kerosene; and cyclic saturated hydrocarbon compounds such as cyclopentane, cyclohexane and cycloheptane. Examples of the aromatic hydrocarbon compounds include benzene, toluene, ethylbenzene, xylene and gasoline fractions. Among these compounds, n-hexane, n-heptane or a gasoline fraction is preferably used. The concentration of the trialkylaluminum salt in the inert solvent is preferably 0.001 to 0.5 mol/L, particularly preferably 0.01 to 0.1 mol/L.
- It is preferred that the production method according to the present invention further comprise the step of adding, before or during the polymerization of the monomer having an ethylenically unsaturated bond, a phosphorus-based antioxidant to at least one of the catalyst system, the polymerization system and the piping in an amount of 0.001 to 3 parts by mass with respect to 100 parts by mass of the polymer obtained by the polymerization.
- Examples of the phosphorus-based antioxidant used in the present invention include known phosphorus-based antioxidants such as triphenyl phosphite, trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,4-di-tert-butyl-5-methylphenyl)phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetra(tridecyl)isopropylidenediphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol)diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-t-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol. Thereamong, a phosphorus-based antioxidant which does not adversely affect the polymerization even when it is added before the polymerization of propylene monomer, such as tris(2,4-di-tert-butylphenyl)phosphite, is preferred.
- In cases where the above-described phosphorus-based antioxidant is used, the phosphorus-based antioxidant is added in an amount of 0.001 to 3 parts by mass, preferably 0.005 to 0.5 parts by mass, with respect to 100 parts by mass of the polymer obtained by the polymerization of a monomer having an ethylenically unsaturated bond. When the amount is less than 0.001 parts by mass, the effect of the addition may not be attained. Meanwhile, the phosphorus-based antioxidant can be added in an amount of 3 parts by mass or greater; however, such an amount is economically disadvantageous because the effect of the addition is small.
- As a method of adding the phosphorus-based antioxidant, the phosphorus-based antioxidant is preferably mixed with the above-described inert solvent before being added, and the phosphorus-based antioxidant may also be mixed in advance with the inert solvent along with the phenolic antioxidant represented by the above-described Formula (1). Alternatively, the phosphorus-based antioxidant may be mixed with the inert solvent and added to the polymerization system, the catalyst system or the piping, separately from the phenolic antioxidant represented by the Formula (1).
- The phenolic antioxidant represented by the above-described Formula (1) which is masked with an organoaluminum compound and the above-described phosphorus-based antioxidant are added in a total amount of preferably 0.001 to 3 parts by mass, more preferably 0.001 to 0.5 parts by mass, with respect to 100 parts by mass of the polymer obtained in the polymerization step.
- Examples of the above-described monomer having an ethylenically unsaturated bond include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcycloalkane, styrene and derivatives of these monomers.
- The monomer used in the present invention which has an ethylenically unsaturated bond may either be a single type of monomer or a combination of two or more types of monomers, and it is preferably ethylene or a combination of α-olefin monomers. The monomer may also be, for example, ethylene by itself, a combination of ethylene and propylene, a combination of ethylene, propylene and butene, or a combination of an α-olefin monomer and a non-conjugated diene monomer.
- As a method of performing the polymerization reaction of the monomer having an ethylenically unsaturated bond, any conventionally used method can be employed. For example, a method of performing polymerization in a liquid phase in the presence of an inert solvent such as an aliphatic hydrocarbon (e.g., butane, pentane, hexane, heptane or isooctane), an alicyclic hydrocarbon (e.g., cyclopentane, cyclohexane or methylcyclohexane), an aromatic hydrocarbon (e.g., toluene, xylene or ethylbenzene), a gasoline fraction or a hydrogenated diesel fraction; a polymerization method in which a liquefied monomer itself is used as a medium; a method of performing polymerization in a gas phase where substantially no liquid phase is present, such as an inert gas atmosphere of nitrogen or the like; or a combination of two or more of these polymerization methods can also be employed. Further, the polymerization may be performed by either a batchwise process or a continuous process, and it may also be performed by a single-step polymerization method or a multi-step polymerization method.
- Moreover, an active hydrogen compound, a particulate carrier, an organoaluminum compound, an ion-exchanging layered compound, an inorganic silicate or a catalyst component other than the above-described polymerization catalyst, such as a carrier, may also be incorporated in such an amount which does not inhibit the polymerization.
- As a polymerization vessel to be used in the above-described polymerization reaction, a continuous reaction vessel installed in an existing polymerization equipment can be used as is. In the present invention, there is no particular restriction on the size, shape, material and the like of the existing polymerization equipment.
- The above-described polymerization catalyst is not particularly restricted and any known polymerization catalyst can be employed. Examples thereof include compounds of transition metals belonging to one of the groups 3 to 11 of the periodic table (such as titanium, zirconium, hafnium, vanadium, iron, nickel, lead, platinum, yttrium and samarium). Representative examples of the polymerization catalyst include Ziegler catalysts; Ziegler-Natta catalysts composed of a titanium-containing solid transition metal component and an organic metal component; Brookhart catalysts, which are compounds in which a hetero atom of nitrogen, oxygen, sulfur, phosphorus or the like is bound to a transition metal belonging to one of the groups 4 to 10 of the periodic table; and metallocene catalysts composed of a transition metal compound belonging to one of the groups 4 to 6 of the periodic table, which has at least one cyclopentadienyl skeleton, and a co-catalyst component. However, an electron-donating compound is preferably employed since a high-quality polymer can be obtained.
- Examples of the above-described Ziegler catalysts include those catalysts that are produced by subjecting a titanium trichloide or titanium trichloride composition, which is obtained by reduction of titanium tetrachloride with organoaluminum or the like, to a treatment with an electron-donating compound and then activating the resultant (see, for example, Japanese Unexamined Patent Application Publication Nos.
S47-34478 S58-23806 S63-146906 S56-100806 S56-120712 S58-104907 S57-63310 S58-157808 S58-83006 S58-5310 S61-218606 S63-43915 S63-83116 - Examples of the above-describe metallocene catalysts include the transition metal metallocene catalyst described in Japanese Unexamined Patent Application Publication No.
H9-12621 H5-043616 H5-295022 H5-301917 H6-239914 H6-239915 H6-239917 H7-082311 H7-228621 H7-330820 H8-059724 H8-085707 H8-085708 H8-127613 H10-226712 H10-259143 H10-265490 H11-246582 H11-279189 H11-349633 2000-229990 2001-206914 2002-37795 2002-194015 2002-194016 PCT Patent Application Laid-open No. 2002-535339 WO 99/37654 WO 99/45014 WO 00/8036 - Examples of the above-described electron-donating compounds include ether-based compounds, ester-based compounds, ketone-based compounds and alkoxysilane-based compounds. These electron-donating compounds may be added individually, or a plurality thereof may be added as required.
- Examples of the above-described ether-based compounds include diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene oxide, tetrahydrofuran, 2,2,5,5-tetramethyl tetrahydrofuran and dioxane.
- Examples of the above-described ester-based compounds include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, ethyl phenylacetate, methyl benzoate, ethyl benzoate, phenyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, methyl methoxybenzoate, ethyl methoxybenzoate, methyl methacrylate, ethyl methacrylate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, γ-butyrolactone and ethyl cellosolve.
- Examples of the above-described ketone-based compounds include acetone, diethyl ketone, methylethyl ketone and acetophenone.
- Examples of the above-described alkoxysilane-based compounds include tetramethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, phenyltrimethoxysilane, cyclohexyltrimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butyl-n-propyldimethoxysilane, t-butylisopropyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, isopropyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltriethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, diisopropyldiethoxysilane, diphenyldiethoxysilane, t-butylmethyldiethoxysilane, cyclohexylmethyldiethoxysilane and dicyclopentyldimethoxysilane.
- The type of the above-described carrier is not restricted and examples thereof include inorganic carriers such as inorganic oxides and organic carriers such as porous polyolefins. A plurality of these carriers may also be used in combination.
- Examples of the above-described inorganic carriers include silica, alumina, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium oxide and zinc oxide. In addition, examples of other inorganic carriers include magnesium halides such as magnesium chloride and magnesium bromide; magnesium alkoxides such as magnesium ethoxide; and ion-exchanging layered compounds.
- The above-described "ion-exchanging layered compounds" refer to those compounds having a crystalline structure in which the surfaces constituted by ionic bonds and the like are laminated in parallel with each other through week bonding force and contain exchangeable ions. Specific examples of such ion-exchanging layered compound include kaolin, bentonite, talc, kaolinite, vermiculite, montmorillonite, mica, α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2·H2O, α-Sn(HPO4)2·H2O and γ-Ti(NH4PO4)2·H2O.
- Examples of the above-described organic carriers include polyesters such as polyethylenes, polypropylenes, polystyrenes, ethylene-butene copolymers, ethylenepropylene copolymers, polymethacrylates, polyacrylates, polyacrylonitriles, polyamides, polycarbonates and polyethylene terephthalates; and polyvinyl chlorides. These organic carriers may also be cross-linked as in the case of, for example, a styrene-divinylbenzene copolymer. Further, catalysts chemically bound to these organic carriers can be used as well.
- These carriers have a particle size (volume average) in the range of usually 0.1 to 300 µm, preferably 1 to 200 µm, more preferably 10 to 100 µm. When the particle size is smaller than 1 µm, the resulting polymer is likely to be in the form of fine powder, while when the particle size is excessively large, coarse particles are generated. Therefore, the particle size of the carrier should be selected in accordance with the desired particle shape.
- The above-described carrier usually has a pore volume of 0.1 to 5 cm2/g, preferably 0.3 to 3 cm2/g. The pore volume can be measured by, for example, a BET method or mercury porosimetry.
- Examples of the above-described organoaluminum compound include the same ones as those exemplified for the organoaluminum compound used in the masking of the above-described phenolic antioxidant represented by the Formula (1).
- In the above-described polymer, as required, other additive(s) that are normally used in a polymer obtained from a monomer having an ethylenically unsaturated bond may also be blended. As a method of blending such other additives, the additives may be added before or at the time of polymerizing the monomer having an ethylenically unsaturated bond, as long as the additives do not inhibit the polymerization. Alternatively, other additives may be mixed with the above-described polymer in an amount appropriate for the intended purpose and the resulting mixture can then be granulated and molded by melt-kneading using a molding apparatus such as an extruder.
- Examples of such other additives include phenolic antioxidants, phosphorus-based antioxidants, thioester-based antioxidants, ultraviolet absorbers, hindered amine compounds, heavy metal inactivators, nucleating agents, flame retardants, metallic soaps, hydrotalcites, fillers, lubricants, antistatic agents, pigments, dyes and plasticizers.
- The above-described phenolic antioxidant is different from the one represented by the above-described Formula (1). Examples of such phenolic antioxidant include 2,6-dit-butyl-4-ethylphenol, 2-t-butyl-4,6-dimethylphenol, styrenated phenol, 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-thiobis-(6-t-butyl-4-methylphenol), 2,2'-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2-methyl-4,6-bis(octylsulfanylmethyl)phenol, 2,2'-isobutylidenebis(4,6-dimethylphenol), iso-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide, 2,2'-oxamide-bis[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2-ethylhexyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, 2,2'-ethylenebis(4,6-di-t-butylphenol), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoate, C13-15 alkyl esters, 2,5-di-t-amylhydroquinone, hindered phenol polymer (AO.OH998, manufactured by ADEKA Palmarole), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, 6-[3-(3-t-butyl-4-hydroxy-5-methyl)propoxy]-2,4,8,10-tetra-t-butylbenzo[d,f][1,3,2]-dioxaphosphepin, hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, calcium bis[monoethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, a reaction product between 5,7-bis(1,1-dimethylethyl)-3-hydroxy-2(3H)-benzofuranone and o-xylene, 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, DL-a-tocophenol (vitamin E), 2,6-bis(α-methylbenzyl)-4-methylphenol, bis[3,3-bis-(4'-hydroxy-3'-t-butyl-phenyl)butyric acid]glycol ester, 2,6-di-t-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl(3,5-di-t-butyl-4-hydroxyphenyl)propionate, distearyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, tridecyl-3,5-di-t-butyl-4-hydroxybenzyl thioacetate, thiodiethylenebis[(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-t-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-t-butylphenol), bis[3,3-bis(4-hydroxy-3-t-butylphenyl)butyric acid]glycol ester, 4,4'-butylidenebis(2,6-di-t-butylphenol), 4,4'-butylidenebis(6-t-butyl-3-methylphenol), 2,2'-ethylidenebis(4,6-di-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, bis[2-t-butyl-4-methyl-6-(2-hydroxy-3-t-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, 2-t-butyl-4-methyl-6-(2-acryloyloxy-3-t-butyl-5-methylbenzyl)phenol, 3,9-bis[2-(3-t-butyl-4-hydroxy-5-methylhydrocinnamoyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane and triethylene glycol-bis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate]. In particular, for example, tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane is preferably used.
- The phenolic antioxidant used as the above-described other additive is added in an amount of 0.001 to 5 parts by mass, more preferably 0.001 to 0.5 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- Examples of the phosphorus-based antioxidant used as the above-described other additive include the same ones as those compounds exemplified in the above as the phosphorus-based antioxidant to be added. The above-described phosphorus-based antioxidant is used in an amount of preferably 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the above-described polymer.
- Examples of the above-described thioester-based antioxidant include tetrakis[methylene-3-(laurylthio)propionate]methane, bis(methyl-4-[3-n-alkyl(C 12/C14)thiopropionyloxy]5-t-butylphenyl)sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl/stearyl thiodipropionate, 4,4'-thiobis(6-t-butyl-m-cresol), 2,2'-thiobis(6-t-butyl-p-cresol) and distearyl-disulfide.
- The thioester-based antioxidant is used in an amount of preferably 0.001 to 0.3 parts by mass, more preferably 0.01 to 0.3 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- Examples of the above-described ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxyphenyl)benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-methylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-tert-octhylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-amyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazole and 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole; 2-(2-hydroxyphenyl)-4,6-diaryl-1,3,5-triazines such as 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(3-C12 to C13 mixed alkoxy-2-hydroxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-acryloyloxyethoxy)phenyl]-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxy-3-allylphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2-hydroxy-3-methyl-4-hexyloxyphenyl)-1,3,5-triazine; benzoates such as phenylsalicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl(3,5-di-tert-butyl-4-hydroxy)benzoate, dodecyl(3,5-di-tert-butyl-4-hydroxy)benzoate, tetradecyl(3,5-di-tert-butyl-4-hydroxy)benzoate, hexadecyl(3,5-di-tert-butyl-4-hydroxy)benzoate, octadecyl(3,5-di-tert-butyl-4-hydroxy)benzoate and behenyl(3,5-di-tert-butyl-4-hydroxy)benzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; cyanoacrylates such as ethyl-α-cyano-β,β-diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and a variety of metal salts and metal chelates, in particular, salts and chelates of nickel and chromium.
- The above-described ultraviolet absorber is used in an amount of 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- Examples of the above-described hindered amine-based light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11 -tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]aminoundecane, bis {4-(1-octyloxy-2,2,6,6-tetramethyl)piperidyl}decanedionate, bis {4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidyl}carbonate and TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals K.K.
- The above-described hindered amine-based light stabilizer is used in an amount of preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- Examples of the above-described heavy metal inactivator include salicylamide-1,2,4-triazol-3-yl, bis-salicylic acid hydrazide, dodecanedioyl-bis(2-(2-hydroxybenzoyl)hydrazide) and bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid)hydrazide. The heavy metal inactivator is used in an amount of preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- Examples of the above-described nucleating agent include metal carboxylates such as sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate and 2-sodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; metal phosphates such as sodium-bis(4-tert-butylphenyl)phosphate, sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate and lithium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate; polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol and bis(dimethylbenzylidene)sorbitol; and amide compounds such as N,N',N"-tris[2-methylcyclohexyl]-1,2,3-propane tricarboxamide (RIKACLEAR PC1), N,N',N"-tricyclohexyl-1,3,5-benzene tricarboxamide, N,N'-dicyclohexyl-naphthalene dicarboxamide and 1,3,5-tri(dimethylisopropoylamino)benzene.
- The above-described nucleating agent is used in an amount of 0.001 to 10 parts by mass, more preferably 0.005 to 5 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- Examples of the above-described flame retardant include aromatic phosphates such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-xylenyl phosphate and resorcinol-bis(diphenylphosphate); phosphonates such as divinyl phenyl phosphonate, diallyl phenyl phosphonate and (1-butenyl)phenylphosphonate; phosphinates such as phenyl diphenylphosphinate, methyl diphenylphosphinate and 9,10-dihydro-9-oxa-10-phosphaphenanthlene-10-oxide derivatives; phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene; phosphorus-based flame retardants such as melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds and red phosphorus; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; and bromine-based flame retardants such as brominated bisphenol A-type epoxy resin, brominated phenol novolac-type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis(pentabromophenyl), ethylenebis-tetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromo bisphenol A-type dimethacrylate, pentabromobenzyl acrylate and brominated styrene.
- The above-described flame retardant is used in an amount of preferably 1 to 70 parts by mass, more preferably 10 to 30 parts by mass, with respect to 100 parts by mass of the above-described polymer.
- Examples of the above-described filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fibers, clays, dolomite, mica, silica, alumina, potassium titanate whiskers, wollastonite and fibrous magnesium oxysulfate. Thereamong, a filler having an average particle size (in the case of a spherical or flat filler) or an average fiber diameter (in the case of a needle-form or fibrous filler) of 5 µm or less is preferred. The amount of the above-described filler to be used can be set as appropriate in a range where the present invention is not adversely affected.
- The above-described lubricant is added for the purpose of imparting the surface of the resulting molded article with lubricity and improving its damage-preventing effect. Examples of such lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; and saturated fatty acid amides such as behenic acid amide and stearic acid amide. These lubricants may be used individually, or two or more thereof may be used in combination.
- The above-described lubricant is added in an amount of 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass, with respect to 100 parts by mass of the above-described polymer. When the amount is less than 0.03 parts by mass, the desired lubricity may not be attained, while when the amount is greater than 2 parts by mass, the lubricant component may bleed out to the surface of the resulting molded article of the polymer and/or cause deterioration in the physical properties thereof.
- The above-described antistatic agent is added for the purpose of reducing the electrostatic property of the resulting molded article and preventing adhesion of dusts caused by electrostatic charge. Examples of the antistatic agent include cationic, anionic and non-ionic antistatic agents. Preferred examples include polyoxyethylene alkylamines, polyoxyethylene alkyl amides, fatty acid esters thereof and glycerin fatty acid esters. These antistatic agents may be used individually, or two or more thereof may be used in combination. Further, the antistatic agent is added in an amount of preferably 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass, with respect to 100 parts by mass of the above-described polymer. When the amount of the antistatic agent is excessively small, the antistatic effect becomes insufficient, while when the amount is excessively large, the antistatic agent may bleed out to the surface and/or cause deterioration in the physical properties of the polymer.
- The method of producing a laminate film according to the present invention is characterized by comprising the step of adding, before or during polymerization of a monomer having an ethylenically unsaturated bond, a phenolic antioxidant represented by the above-described Formula (1), which is masked with an organoaluminum compound, to at least one of a catalyst system, a polymerization system and a piping, such that the phenolic antioxidant is incorporated in an amount of 0.001 to 0.5 parts by mass with respect to 100 parts by mass of a polymer obtained by the polymerization. By this constitution, sufficient stabilization effect can be attained with an addition of the phenolic antioxidant in a small amount and, as a result of the reduction in the added amount, it became possible to prevent the antioxidant from bleeding out and eliminate adhesion-inhibiting factors generated in an ozone treatment. A phenolic antioxidant other than the specific phenolic antioxidant according to the present invention exhibits poor stabilization effect when added at the time of polymerization; therefore, such a phenolic antioxidant is required to be added in a large amount. Consequently, the antioxidant bleeds out to inhibit the adhesion of a laminate film. The resulting polymer can be molded into a laminate film by a known method. Examples of a method of processing the above-described polymer into a laminate film include a method in which the above-described polymer is molded into films and a laminate film is produced by laminating the films with each other or by laminating the film(s) with a laminate base material. Further, as required, the above-described polymer may also be processed into a laminate film having three or more layers.
- Examples of the above-described laminate base material include those that are normally used by being adhered with a film, such as polymers having a film-forming capability, papers, nonwoven fabrics, metal foils (e.g., aluminum foils), metal-deposited films (e.g., silicon oxide-deposited films and aluminum-deposited films) and cellophanes.
- The thickness of the above-described laminate base material is not particularly restricted and can be selected as appropriate in accordance with the purpose thereof. The thickness of the above-described laminate base material may be generally about 5 to 50 µm. Further, as required, the laminate base material may be subjected to a surface treatment such as an ozone treatment, a corona discharge treatment or a flame treatment.
- Examples of the polymers having a film-forming capability that can be used as the above-described laminate base material include olefin-based copolymers such as high-density polyethylenes, medium/low-density polyethylenes, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, ionomers, polypropylenes, poly-1-butene and poly-4-methyl1-pentene; vinyl-based polymers such as polyvinyl chlorides, polyvinylidene chlorides, polystyrenes, polyacrylates and polyacrylonitriles; polyamides such as nylons and polymetaxylylene adipamide; polyesters such as polyethylene terephthalates, polyethylene isophthalates, polybutylene terephthalates and polyethylene naphthalates; polyvinyl alcohols; ethylene-vinyl alcohol copolymers; and polycarbonates. Further, films obtained by molding these polymers may also be stretched uniaxially or biaxially.
- Among those polymers that are produced by the production method according to the present invention, polyethylenes are preferred. In particular, a linear low-density polyethylene (LLDPE) is preferred since it has excellent heat-seal property and heat resistance and exhibits resistance to bending and rubbing when made into a packaging material.
- The thickness of the laminate film produced by the production method according to the present invention is not particularly restricted and can be selected as appropriate in accordance with the purpose thereof. The thickness of the laminate film may be generally 10 to 200 µm.
- As a method of laminating the above-described film and the laminate base material, for example, a dry lamination method, an extrusion lamination method, a hot-melt lamination method, a wet lamination method, a wax lamination method or a thermal lamination method can be employed.
- The above-described dry lamination method is a method in which an adhesive diluted with an organic solvent to an appropriate viscosity is coated onto a film and this film is dried and then laminated with the other film by press-adhesion. As the adhesive, one composed of a base agent and a curing agent is commonly used. Examples of the base agent include ester compounds composed of isophthalic acid, adipic acid, sebacic acid or the like and ethylene glycol, neopentyl glycol, 1,6-hexane diol or the like; polyester-urethane diol resins composed of isophorone diisocyanate, xylylene diisocyanate, or hexamethylene diisocyanate; silane coupling agents; and epoxy-resin containing agents.
- Examples of the curing agent include those that are composed of trimethylolpropane and isophorone diisocyanate, xylylene diisocyanate or hexamethylene diisocyanate. However, the base agent and the curing agent are not restricted to the ones exemplified in the above and they can be selected as appropriate in accordance with the intended purpose of providing heat resistance, or chemical resistance.
- Examples of the above-described extrusion lamination method include a method of producing a poly-laminate by coating molten polyethylene onto one side of a film and a method of producing a poly-sandwich laminate by pouring molten polyethylene between two films. The molten polyethylene serves as an adhesive; however, polypropylene may be used in place of polyethylene. Further, in cases where an anchor coating agent is applied to the surface of a film, a paper and a thick film can also be easily laminated thereon.
- Examples of the above-described anchor coating agent include adhesives for epoxy resins, such as carboxylic acid anhydride-modified polyolefins, isocyanate-based resins, organic titanate-based resins and polyethylene imine-based resins and polybutadiene-based resins; however, an isocyanate-based resin having excellent water resistance, moisture resistance and boiling resistance is preferably employed.
- The above-described hot-melt lamination method is a method in which an adhesive or the like, which is adjusted by heating to have an appropriate viscosity, is coated onto a film and this film press-adhered. This method is advantageous in that it includes no drying step and the resulting laminate can be used immediately after being cooled; however, the method has drawbacks in that, for example, the resulting laminate is poor in heat resistance and strength.
- The above-described wet lamination method is a method of laminating using a water-soluble or emulsion-type adhesive. Examples of the water-soluble or emulsion-type adhesive include water-soluble vinylons and vinyl acetate-based emulsions.
- The above-described thermal lamination method is a method capable of adhering the film only by press-adhesion with application of heat thereto. This method is advantageous in that it does not require an adhesive, a solvent and the like to be used; however, since the resulting laminate has poor heat resistance as a packaging material, the use thereof is limited.
- The use of the laminate film obtained by the production method of the present invention is not particularly restricted and the laminate film can be generally utilized in those applications where a laminate film is conventionally used.
- Examples thereof include the uses as food packaging materials in the form of a laminate film having an olefin film highly resistant to water as an outer layer or a laminate obtained by laminating a low-density polyethylene, a medium-density polyethylene, an ethylene-vinyl acetate copolymer or the like. Further, in cases where the laminate film is utilized as a boil-in-bag pouch or a retort pouch packaging material, for example, an oxygen impermeable film such as an aluminum foil is laminated as an inner layer.
- As described in the above, the method of producing a resin composition for a coated member according to the present invention is characterized by comprising the steps (A) and (B). In other steps such as the step of preparing a catalyst, the step of feeding a monomer which is a starting material, the step of polymerizing the monomer and the step of recovering the resulting polymer, those method that are known in the method of polymerization a monomer having an ethylenically unsaturated bond can be employed. Hereinafter, these steps will each be described in detail. It is noted here that the term "coated member" used in the present invention refers to a member obtained by coating a molded article of a resin composition.
- The step (A) is a step of adding, before or during polymerization of a monomer having an ethylenically unsaturated bond, a phenolic antioxidant represented by the above-described Formula (1), which is masked with an organoaluminum compound, to at least one of a catalyst system, a polymerization system and a piping, such that the above-described phenolic antioxidant is incorporated in an amount of 0.001 to 0.5 parts by mass with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and a thermoplastic elastomer.
- Specific examples of the structure of the phenolic antioxidant represented by the Formula (1) include the above-described compounds No. 1 to No. 16. However, the present invention is not restricted to the above-described compounds by any means.
- The phenolic antioxidant represented by above-described Formula (1), which is masked with an organoaluminum compound, is added such that the amount of the phenolic antioxidant (that is, the amount of the phenolic antioxidant by itself prior to being masked) becomes preferably 0.001 to 0.5 parts by mass, more preferably 0.001 to 0.3 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and a thermoplastic elastomer.
- When the amount of the phenolic antioxidant is less than 0.001 parts by mass, a desired stabilization effect may not be attained, while when the amount is greater than 0.5 parts by mass, the phenolic antioxidant may bleed out to the surface of the resulting molded article to cause the outer appearance.
- It is noted here that, in cases where the phenolic antioxidant represented by above-described Formula (1), which is masked with an organoaluminum compound, is added before or during polymerization of a monomer performed to obtain a thermoplastic elastomer, the phenolic antioxidant is added such that the total amount of the phenolic antioxidant added in the step (A) and in the synthesis of the thermoplastic elastomer is in the above-described range.
- As for a method of adding the phenolic antioxidant represented by the above-described Formula (1) which is masked with an organoaluminum compound, there is no particular restriction. Examples of suitable mode thereof include one in which the masked phenolic antioxidant is added and mixed in at least one of a catalyst feed tank, a polymerization apparatus and a production line.
- The above-described masking can be performed by mixing and stirring an organoaluminum compound and the phenolic antioxidant in an inert solvent. By the mixing and stirring, the hydrogen of the phenolic hydroxyl group of the phenolic antioxidant is substituted with the organoaluminum compound. The above-described phenolic antioxidant and organoaluminum compound may be mixed with stirring prior to being added to at least one of the catalyst system, the polymerization system and the piping. Alternatively, the phenolic antioxidant and the organoaluminum compound may be added and mixed separately in at least one of the catalyst system, the polymerization system and the piping.
- In cases where a compound produced as a by-product in the masking reaction of the phenolic antioxidant does not affect the polymerization reaction of the monomer or the resulting polymer, the masked phenolic antioxidant may be used as is; however, in cases where the by-produced compound has an effect, it is preferred to remove the compound by vacuum distillation or the like before adding the masked phenolic antioxidant to at least one of the catalyst system, the polymerization system and the piping.
- It is desired that the above-described masked phenolic antioxidant be capable of undergoing a reaction with a hydrogen-donating compound such as water, an alcohol or an acid, which is added as a deactivation treatment of the polymerization catalyst after the polymerization, and be thereby regenerated.
- Examples of the above-described organoaluminum compound include the same ones as those exemplified in the above.
- It is preferred that the mixing ratio of the organoaluminum compound and the phenolic antioxidant represented by the above-described Formula (1) (the organoaluminum compound/the phenolic antioxidant represented by the above-described Formula (1)) be, in terms of mass ratio, 1/5 to 100/1. When the ratio of the organoaluminum compound is lower than 1/5, the excessive amount of the phenolic antioxidant may adversely affect the catalyst activity, while when the ratio is higher than 100/1, an aluminum compound remains in the resulting polymer after the polymerization and this may cause deterioration in the physical properties of the polymer or affect the component ratio of the catalyst metal, making it unable to perform the desired polymerization.
- Examples of the above-described inert solvent include the same ones as those exemplified in the above. The concentration of the organoaluminum compound in the inert solvent is in the range of preferably 0.001 to 0.5 mol/L, particularly preferably 0.01 to 0.1 mol/L.
- It is preferred that the method of producing a resin composition for a coated member according to the present invention further comprise the step of adding, before or during the polymerization of the monomer having an ethylenically unsaturated bond, a phosphorus-based antioxidant to at least one of the catalyst system, the polymerization system and the piping. The phenolic antioxidant represented by the above-described Formula (1) and the phosphorus-based antioxidant may be added separately, or they may be mixed in advance before being added.
- The phosphorus-based antioxidant may also be added at the time of the polymerization of the below-described thermoplastic elastomer (before or during the polymerization of a monomer).
- Examples of the above-described phosphorus-based antioxidant include the same ones as those exemplified in the above.
- The above-described phosphorus-based antioxidant is used in an amount of preferably 0.001 to 3 parts by mass, more preferably 0.005 to 0.5 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- In cases where the above-described phosphorus-based antioxidant is added in the addition step, the phosphorus-based antioxidant is preferably mixed with the above-described inert solvent; however, the phosphorus-based antioxidant may also be mixed in advance with the inert solvent along with the phenolic antioxidant represented by the above-described Formula (1). Alternatively, the phosphorus-based antioxidant may be mixed with the inert solvent and added to the polymerization system, the catalyst system or the piping, separately from the phenolic antioxidant represented by the Formula (1).
- Examples of the above-described monomer having an ethylenically unsaturated bond include the same ones as those exemplified in the above.
- In the method of producing a resin composition for a coated member according to the present invention, the monomer to be used which has an ethylenically unsaturated bond may either be a single type of monomer or a combination of two or more types of monomers, and it is preferably ethylene or a combination of α-olefin monomers. The monomer may also be, for example, ethylene by itself, a combination of ethylene and propylene, a combination of ethylene, propylene and butene, or a combination of an α-olefin monomer and a non-conjugated diene monomer.
- Examples of a method of performing the polymerization reaction of the monomer having an ethylenically unsaturated bond include the same ones as those exemplified in the above.
- As a polymerization vessel to be used in the above-described polymerization reaction, a continuous reaction vessel installed in an existing polymerization equipment can be used as is. In the present invention, there is no particular restriction on the size, shape, material and the like of the existing polymerization equipment.
- Examples of a polymerization catalyst used in the above-described polymerization reaction include the same ones as those exemplified in the above.
- Further, the polymerization reaction may also be performed in the presence of an active hydrogen compound, an organoaluminum compound, an ion-exchanging layered compound, an inorganic silicate or a catalyst component other than the above-described polymerization catalyst, such as a carrier, in such an amount which does not inhibit the polymerization.
- Examples of the above-described carrier include the same ones as those exemplified in the above.
- Examples of the above-described ion-exchanging layered compound include the same ones as those exemplified in the above.
- Examples of the above-described organic carrier include the same ones as those exemplified in the above.
- The carrier has a particle size (volume average) in the range of usually 0.1 to 300 µm, preferably 1 to 200 µm, more preferably 10 to 100 µm. When the particle size is smaller than 1 µm, the resulting polymer is likely to be in the form of fine powder, while when the particle size is excessively large, coarse particles are generated. Therefore, the particle size of the carrier is preferably selected in accordance with the desired particle shape.
- The above-described carrier usually has a pore volume of 0.1 to 5 cm2/g, preferably 0.3 to 3 cm2/g. The pore volume can be measured by, for example, a BET method or mercury porosimetry.
- Examples of the above-described organoaluminum compound include the same ones as those exemplified for the organoaluminum compound used to mask the phenolic antioxidant represented by the Formula (1).
- In the present invention, as required, other additive(s) that are normally used in a polymer obtained from a monomer having an ethylenically unsaturated bond may also be blended. As a method of blending such other additives, the additives may be added at the time of polymerizing the monomer having an ethylenically unsaturated bond, as long as the additives do not inhibit the polymerization. Alternatively, other additives may be mixed with the above-described polymer in an amount appropriate for the intended purpose and the resulting mixture can then be granulated and molded by melt-kneading using a molding apparatus such as an extruder.
- The step (B) is a step of melt-kneading the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond with the thermoplastic elastomer. In the step (B), it is preferred that the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer be melt-kneaded at a mass ratio (the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond/the thermoplastic elastomer) of 2/1 to 4/1. When the ratio of the thermoplastic elastomer is lower than 4/1, the adhesion with a coating film may be deteriorated, while when the ratio is higher than 2/1, coloration of the resultant may easily occur.
- The above-described "thermoplastic elastomer" refers to a macromolecular material which can be plasticized (fluidized) at a high temperature and processed like a plastic and exhibits properties of a rubber elastic body (elastomer) at normal temperature. A thermoplastic elastomer is composed of a hard segment (plastic component) and a soft segment (elastic component) and has, for example, a block polymer-type structure in which a hard segment and a soft segment are chemically bound in a single polymer to form a block copolymer or a blend-type structure called "sea-island dispersion" or "polymer alloy", which is obtained by physically mixing a polymer constituting a hard segment and a polymer constituting a soft segment.
- A block polymer-type thermoplastic elastomer can be produced by block copolymerization. In the case of a blend-type thermoplastic elastomer composition, after producing a soft segment and a hard segment, the thus obtained hard segment and soft segment are physically dispersed using a kneader such as a Banbury mixer or a biaxial extruder, thereby a blend-type thermoplastic elastomer composition can be obtained.
- In the present invention, when a block polymer-type thermoplastic elastomer is used, the block copolymer is preferably a copolymer of ethylene and an α-olefin. Examples of the α-olefin include α-olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene and 1-octene. These α-olefins may be used individually, or two or more thereof may be used in combination.
- Further, in cases where a block polymer-type thermoplastic elastomer is produced, a segment originated from a monomer other than ethylene and α-olefin may also be incorporated. Examples of such other monomer include non-conjugated dienes having 5 to 15 carbon atoms, such as dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene and 1,5-dicyclooctadiene; vinyl ester compounds such as vinyl acetate; ethylenically unsaturated carboxylic acid ester compounds such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate and butyl acrylate; and vinylnitrile compounds such as acrylonitrile and methacrylonitrile. These other monomers may be used individually, or two or more thereof may be used in combination. Alternatively, these other monomers may be (co-)polymerized as well.
- Examples of blend-type thermoplastic elastomer suitably used in the present invention include those which contain an olefin resin as a hard segment and an olefin-based copolymer elastomer as a soft segment.
- Examples of the above-described olefin resin contained as a hard segment include low-density polyethylenes, high-density polyethylenes, linear high-density polyethylenes, linear low-density polyethylenes, branched low-density polyethylenes, ethylene homopolymers, propylene homopolymers, and copolymers of ethylene and an α-olefin. Examples of the α-olefin include α-olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene. The above-described olefin resins may be used individually, or two or more thereof may be used in combination.
- As the above-described olefin-based copolymer elastomer contained as a soft segment, an elastomer which is a copolymer of ethylene and an α-olefin is preferably used. As the above-described α-olefin, for example, an α-olefin having 3 to 10 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene or 1-octene, is usually used. The above-described may be used individually, or two or more thereof may be used in combination.
- Further, in the case of a blend-type thermoplastic elastomer, the soft segment may also contain other elastomer along with the olefin-based copolymer elastomer, as long as it does not deteriorate the effects of the present invention. As such other elastomer, for example, a styrene-based elastomer such as polybutadiene, hydrogenated polybutadiene or hydrogenated polyisoprene; a polyvinyl chloride-based elastomer; a polyester-based elastomer such as polyether; a polyurethane-based elastomer; a nylon-based elastomer; or an elastic polymer such as natural rubber can be used.
- In the above-described blend-type thermoplastic elastomer, the mass ratio of the hard segment and the soft segment can be set as appropriate in accordance with the desired purpose.
- The catalyst used in the production of the thermoplastic elastomer according to the present invention is not particularly restricted and any known polymerization catalyst can be employed. Alternatively, the polymerization catalyst exemplified in the above to be used in the polymerization of a monomer having an unsaturated bond may also be employed.
- As a method of performing the polymerization reaction, the method exemplified in the above to be used for performing the polymerization reaction of a monomer having an ethylenically unsaturated bond can be employed.
- In the thermoplastic elastomer according to the present invention, in addition to the olefin resin and olefin-based copolymer, other component(s) such as other resin, a rubber, a cross-linking agent, a cross-linking auxiliary, a compatibilizing agent, a lubricant, an antistatic agent, a softening agent and/or a foaming agent may be blended as well. It is preferred that the above-described other component(s) be blended prior to the step of melting the thermoplastic elastomer and the above-described polymer obtained by the monomer having an ethylenically unsaturated bond; however, the above-described other component(s) may also be blended simultaneously with the melting step.
- Examples of the above-described other resin include ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer, polyamide, poly(4-methyl-1-pentene), styrene-isoprene-styrene block copolymer, styrene-ethylenebutene-styrene block copolymer, styrene-ethylenepropylene-styrene block copolymer and styrene-butadienestyrene block copolymer.
- The above-described rubber is not particularly restricted, and it may be, for example, an amorphous random elastic copolymer which contains an olefin-derived repeating unit in an amount of not less than 50% of the high-molecular-weight component in the rubber.
- Examples of such elastic copolymer include copolymers that are obtained by copolymerizing a combination of two or more monomers selected from the group consisting of ethylene and α-olefins having 3 to 10 carbon atoms. Further, the elastic copolymer may also be one which is obtained by copolymerizing a combination of two or more monomers selected from the group consisting of ethylene and α-olefins having 3 to 10 carbon atoms with a conjugated diene monomer and/or a non-conjugated diene monomer.
- Examples of the above-described α-olefins having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene and 1-octene.
- Examples of the above-described conjugated diene include butadiene, isoprene and chloroprene.
- Examples of the above-described non-conjugated diene monomer include dicyclopentadiene, 1,4-hexadiene, 1,5-cyclooctadiene, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene.
- Examples of the above-described cross-linking agent include organic peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-di(t-butylperoxy)3,5,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(peroxybenzoyl)hexyne-3 and dicumyl peroxide.
- The above-described organic peroxide is added in an amount of 0.005 to 2.0 parts by mass, preferably 0.01 to 0.6 parts by mass, with respect to 100 parts by mass of the thermoplastic elastomer. When the amount is less than 0.005 parts by mass, the effect of crosslinking reaction is limited, while when the amount is greater than 2.0 parts by mass, it becomes difficult to control the reaction and such a large amount is thus economically disadvantageous. Further, the organic peroxide may be mixed with a diluent to be used in the form of a liquid or powder substance.
- Examples of the diluent include oils, organic solvents and inorganic fillers (such as silica and talc).
- Examples of the above-described cross-linking auxiliary include those which are capable of increasing the crosslinking degree of a crosslinked-type thermoplastic elastomer and thus improving the physical properties of the resulting thermoplastic elastomer composition, and a cross-linking auxiliary which has a plurality of double bonds in the molecule is preferably used.
- Examples of such cross-linking auxiliary include tetraethylthiuram disulfide (TETD), tetramethylthiuram disulfide (TMTD), N,N'-m-phenylenebismaleimide, toluylenebismaleimide, p-quinonedioxime, nitrobenzene, diphenylguanidine, divinylbenzene, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allylmethacrylate. These cross-linking auxiliaries may be used individually, or a plurality thereof may be used in combination.
- The above-described cross-linking auxiliary is added in an amount of preferably 0.01 to 4.0 parts by mass, more preferably 0.05 to 2.0 parts by mass, with respect to 100 parts by mass of the thermoplastic elastomer. When the amount is less than 0.01 parts by mass, the effect of the addition may not be easily attained, while an amount of greater than 4 parts by mass may be economically disadvantageous.
- In cases where the thermoplastic elastomer is cross-linked using an electron beam, it is desired that the irradiation dose of the electron beam be 1 kGray to 100 kGray. When the irradiation dose is less than 1 kGray, the moldability of the thermoplastic elastomer may be poor when it is melted, while when the irradiation dose is 100 kGray or greater, the molecular chain may be broken and/or the resultant may become sticky.
- In the thermoplastic elastomer composition according to the present invention, in order to improve the interfacial adhesion between the polyolefin resin and crosslinked rubber, a compatibilizing agent may be added as well. Examples of the compatibilizing agent include silane coupling agents such as silane-modified olefin resins and silane-modified olefin-based rubbers; and adhesive resins (e.g., polystyrene-polybutadiene-polystyrene block copolymers, polyolefin-based grafts and comb-type grafts).
- Examples of the above-described lubricant include the same ones as those exemplified in the above. The above-described lubricant is added in an amount of preferably 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass, with respect to 100 parts by mass of the thermoplastic elastomer. When the amount is less than 0.03 parts by mass, the desired lubricity may not be attained, while when the amount is greater than 2 parts by mass, the lubricant component may bleed out to the surface of the resulting molded article of the thermoplastic elastomer composition and/or cause deterioration in the physical properties thereof.
- Examples of the above-described antistatic agent include the same ones as those exemplified in the above. Further, the antistatic agent is added in an amount of preferably 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass, with respect to 100 parts by mass of the thermoplastic elastomer. When the amount of the antistatic agent is excessively small, the antistatic effect is insufficient, while when the amount is excessively large, the antistatic agent may bleed out to the surface and/or cause deterioration in the physical properties of the thermoplastic elastomer composition.
- Examples of the above-described softening agent include process oils and aliphatic cyclic saturated hydrocarbon resins.
- Examples of the above-described foaming agent include volatile foaming agents composed of a lower aliphatic hydrocarbon such as propane, butane or pentane, a lower alicyclic hydrocarbon such as cyclobutane or cyclopentane, and a halogenated hydrocarbon such as monochlorodifluoromethane, dichlorodifluoromethane, trichlorodifluoroethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, methyl chloride, ethyl chloride or methylene chloride; gaseous foaming agents such as nitrogen, carbon dioxide gas, oxygen and air; pyrolytic foaming agents composed of sodium bicarbonate, ammonium bicarbonate, dinitrosopentamethylenetetramine, toluenesulfonyl hydrazide, azodicarbonamide, p,p'-oxybisbenzenesulfonylhydrazide, azobisisobutyronitrile or the like. Thereamong, a pyrolytic foaming agent is particularly desirably used.
- The amount of the foaming agent to be used is appropriately selected as required.
- Mixing of the above-described thermoplastic elastomer and foaming agent is carried out inside an extruder or the like by kneading them while melting the thermoplastic elastomer; however, in cases where a pyrolytic foaming agent is used, it may be mixed with the thermoplastic elastomer in advance before feeding the thermoplastic elastomer to an extruder or the like. Alternatively, the pyrolytic foaming agent may be fed to an extruder or the like separately from the thermoplastic elastomer. Further, in cases where a volatile foaming agent or a gaseous foaming agent is used, for example, the foaming agent may be injected into molten thermoplastic elastomer from the middle section of a screw of a vent-type extruder or the like.
- In cases where a foaming agent is used in the thermoplastic elastomer, the thermoplastic elastomer and the foaming agent are extrusion-foamed via a die installed at the tip of an extruder. The shape of the resulting foamed article is arbitrary and it is not particularly restricted; however, the foamed article may be in the form of, for example, a film, a sheet, a pipe or a cylinder.
- In the resin composition for a coated member according to the present invention, as required, other additive(s) may also be blended. As a method of blending other additives, the additives may be added at the time of polymerizing the monomer having an ethylenically unsaturated bond or polymerizing the thermoplastic elastomer, as long as the additives do not inhibit the polymerization. Alternatively, other additives may be blended and uniformly dispersed in an amount appropriate for the intended purpose at the time of melt-kneading the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer. Here, in cases where other additives are added, it is preferred that the thermoplastic elastomer composition be prepared by kneading or stirring until a uniform composition is attained using a biaxial extruder equipped with a heating device, a Banbury mixer, a pressure kneader, a Henschel mixer, a Brabender kneader, disperser or the like.
- Examples of the above-described other additives that may be blended in the resin composition for a coated member according to the present invention include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, ultraviolet absorbers, hindered amine compounds, heavy metal inactivators, nucleating agents, flame retardants, metallic soaps, hydrotalcites, fillers, lubricants, antistatic agents, pigments, dyes and plasticizers.
- Examples of the above-described phenolic antioxidants include the same ones as those exemplified in the above and phenolic antioxidants represented by the above-described Formula (1); however, tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane is particularly preferably used since it is relatively inexpensive and has good cost performance.
- The phenolic antioxidant used as the above-described other additive is added in an amount of preferably 0.001 to 0.5 parts by mass, particularly preferably 0.01 to 0.3 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- Examples of the above-described phosphorus-based antioxidants include the same ones as those compounds exemplified in the above as the phosphorus-based antioxidant to be added. The above-described phosphorus-based antioxidant is used in an amount of preferably 0.01 to 0.3 parts by mass with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- Examples of the above-described sulfur-based antioxidants include the same ones as those exemplified in the above for the thioester-based antioxidant to be added. The sulfur-based antioxidant is used in an amount of preferably 0.01 to 0.3 parts by mass with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- Examples of the above-described ultraviolet absorbers include the same ones as those exemplified in the above.
- The ultraviolet absorber is used in an amount of 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- Examples of the above-described hindered amine-based light stabilizers include the same ones as those exemplified in the above.
- The hindered amine-based light stabilizer is used in an amount of 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- Examples of the above-described nucleating agents include the same ones as those exemplified in the above.
- The nucleating agent is used in an amount of 0.001 to 10 parts by mass, more preferably 0.005 to 5 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- Examples of the above-described flame retardants include the same ones as those exemplified in the above.
- The flame retardant is used in an amount of 1 to 70 parts by mass, more preferably 10 to 30 parts by mass, with respect to a total of 100 parts by mass of the polymer obtained by the polymerization of the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer.
- Examples of the above-described fillers include the same ones as those exemplified in the above.
- Examples of the above-described lubricants include the same ones as those exemplified in the above.
- Examples of the above-described antistatic agents include the same ones as those exemplified in the above.
- As for a method of molding the polymer obtained by the present invention, there is not particular restriction, and the polymer can be molded by a known molding method such as extrusion molding, injection molding, hollow molding, blow molding or compression molding.
- The coated member obtained by the present invention can be used in the form of, for example, but not limited to, a film, a sheet, a cylinder, a box or a sphere. Specific examples of the use of the coated member include automobile exterior parts where the outer appearance of the paint surface is given high importance, such as a bumper, a spoiler, a side guard molding or a radiator grill.
- The present invention will now be described in more detail by way of examples and comparative examples thereof; however, the present invention is not restricted thereto by any means. The evaluations in the examples and comparative examples were performed by the following methods.
- After producing a laminate film, the presence or absence of detachment of the film was verified. Specifically, when both ends of the laminate film was rubbed, a condition where the laminate film easily slipped out of place was evaluated as "could not be adhered" and a condition where the laminate film stayed in place was evaluated as "good".
- From a laminate film obtained by the below-described procedures, a test piece of 15 mm in width and 100 mm in length was prepared. After manually abrasing the thus obtained test piece over a length of 50 mm in the longitudinal direction, both ends of the resulting test piece was pinched and detached in the 180-degree direction using a tensile tester (STROGRAPH APII, manufactured by Toyo Seiki Seisaku-sho, Ltd.) at a tensile rate of 300 mm/min to measure the maximum strength as adhesion strength.
- From a laminate film obtained by the below-described procedures, a packaging bag of 130 mm × 170 mm was prepared and, as a content, 200 ml of water was enclosed in the packaging bag. The packaging bag was then subjected to a hot water-stationary retort sterilization treatment at 120°C for 30 minutes. After the sterilization treatment, the packaging bag was cooled to room temperature and its content, water, was mixed with chloroform to be extracted into chloroform, followed by concentration. Thereafter, using a gas chromatograph-mass spectrometer, low-molecular weight substances, such as the blended additives and their oxides and decomposed matters, were quantified to determine the eluted amount of each blended additives. The ratio of the eluted amount of each additive with respect to the blended amount was calculated to determine the ratio of elution.
- From a laminate film obtained by the below-described method, two test pieces of 40 mm in width and 100 mm in length were prepared and laminated such that the tip of one of the test pieces in the longitudinal direction overlaps with the tip of the other test piece in the longitudinal direction by 15 mm. Then, the thus laminated test pieces were heat-sealed at 200°C and 1 kg/cm2 for 1 second. Using a tensile tester, the thus heat-sealed test pieces were detached in the 180-degree direction at a tensile rate of 300 mm/min to measure the tensile strength as heat-seal strength.
- After preparing a homogeneous solution by allowing 4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexyl alcohol to react with heating at 130°C for 2 hours, 1.11 g (7.5 mmol) of phthalic anhydride was added to the thus obtained homogeneous solution and the resulting mixture was further allowed to react with stirring at 130°C for 1 hour, thereby dissolving phthalic anhydride in the homogeneous solution. The resulting homogeneous solution was cooled to room temperature and the entire amount thereof was then dropwisely charged to 200 ml (1.8 mol) of titanium tetrachloride, which had been kept at -20°C, over a period of 1 hour. Thereafter, the resultant was heated to 110°C over a period of 4 hours and once the temperature reached 110°C, 2.68 ml (12.5 mmol) of diisobutyl phthalate was added and the resulting mixture was allowed to react for 2 hours with stirring while maintaining the temperature at 110°C. After completion of the reaction, the resulting solids were recovered by hot filtration and suspended in 200 ml of titanium tetrachloride, and the suspension was allowed to react with heating at 110°C for 2 hours. Thereafter, the resulting solids were recovered again by hot filtration and thoroughly washed with 110°C decane and hexane until no free titanium compound was detected in the washings, thereby obtaining a solid Ti catalyst component.
- The solid Ti catalyst component obtained by the above-described method was stored in the form of a heptane slurry with an addition of heptane to a concentration of 5 mg/mL. When a portion of the heptane slurry was recovered and dried and the catalyst composition was analyzed, the solid Ti catalyst component was determined to have the following composition: 2.9% by mass of titanium, 56.0% by mass of chlorine, 17.0% by mass of magnesium and 20.9% by mass of isobutyl phthalate.
- In a flask whose atmosphere had been replaced with nitrogen, 10 mL of dry heptane, 54 mg of triethylaluminum and 161 mg of the respective phenolic antioxidant shown in Tables 1 to 3 were mixed with stirring to mask the phenolic antioxidant, thereby preparing a phenoxide solution having a phenolic antioxidant concentration of 16 mg/mL.
- In a flask whose atmosphere had been replaced with nitrogen, 144 mg of the respective phosphorus-based antioxidant shown in Tables 1 to 3 and 6 mL of heptane were added and mixed with stirring to prepare a phosphite solution having a phosphorus-based antioxidant concentration of 24 mg/mL.
- To a 1,000-ml autoclave whose atmosphere had been replaced with nitrogen, 600 ml of dry heptane, 0.41 g (3.6 mmol) of triethylaluminum and, in those Examples and Comparative Examples for which the addition method is indicated as "at the time of polymerization" in Tables 1 to 3, the thus obtained phenoxide solution and phosphite solution were added in such a manner to attain the respective formulations of stabilizer composition shown in Tables 1 to 3. Then, 82.23 mg (0.36 mmol) of dicyclopentadimethoxysilane and the heptane slurry of the solid Ti catalyst component (0.012 mmol in terms of Ti) were sequentially added. Further, 11.2 g of 1-hexene was added and the atmosphere inside the autoclave was replaced with ethylene so as to pressurize the system with ethylene at 1 kgf/cm2G, thereby performing pre-polymerization (600 rpm) at 50°C for 5 minutes. Thereafter, ethylene was purged and then, hydrogen, ethylene and, as an ethylene mixture, 1-hexene were introduced to the autoclave such that the hydrogen partial pressure and the ethylene partial pressure became 2 kgf/cm2G and 7 kgf/cm2G, respectively and the amount of 1-hexene became 7 wt%. After raising the temperature of the autoclave to 80°C, the atmosphere inside the autoclave was pressurized with propylene at 5 kgf/ cm2G to perform polymerization reaction at 80°C for 2 hours. After replacing the atmosphere inside the system with nitrogen gas and quenching the polymerization reaction by adding 5 mL of ethanol at 40°C, the solvent was removed under reduced pressure at 50°C and the resulting polymer was dried in vacuum at 40°C for 5 hours to obtain a polyethylene powder.
- To 100 parts by mass of the thus obtained powder, in those Examples and Comparative Examples for which the addition method is indicated as "at the time of granulation" in Tables 1 to 3, the stabilizer composition(s) shown in Tables 1 to 3 and 0.05 parts by mass of calcium stearate were added and mixed. Then, the resulting mixture was extruded from a T-die at an extrusion temperature of 250°C to mold a film sheet of 60 µm in thickness and 300 mm in width. Thereafter, onto a supporting substrate (ester film, manufactured by TOYOBO Co., Ltd.; trade name: TOYOBO ESTER FILM E5100), an anchor coating agent (manufactured by TOYO INK Co., Ltd.; trade name: ORIBAIN TX1439) was coated in the amount shown in Table 1 and the coated surface and the above-described film sheet were press-adhered using a mat roll to produce a laminate film.
[Table 1] Outer member Amount of applied anchor coating agent [g/m2] Stabilizer Added amount [parts by mass] Method of addition Adhesion Ratio of elution Example 1-1 E-5100 0.10 AO-11) 0.0150 at the time of polymerization4) good 0.3 Example 1-2 E-5100 0.10 AO-11) 0.0030 at the time of polymerization4) good 0.2 P-13) 0.0060 Example 1-3 E-5100 0.10 AO-11) 0.0030 at the time of polymerization4) good 0.4 P-13) 0.030 at the time of granulation5) Comparative Example 1-1 E-5100 0.10 AO-11) 0.0150 at the time of granulation5) film could not be molded Comparative Example 1-2 E-5100 0.10 AO-22) 0.0030 at the time of polymerization4) film could not be molded P-13) 0.0060 at the time of granulation5) Comparative Example 1-3 E-5100 0.10 AO-11) 0.0030 at the time of granulation5) film could not be molded P-13) 0.0060 at the time of polymerization4) Comparative Example 1-4 E-5100 0.10 AO-22) 0.030 at the time of polymerization4) film could not be molded P-13) 0.030 Comparative Example 1-5 E-5100 0.10 AO-11) 0.0030 at the time of granulation5) film could not be molded P-13) 0.0060 Comparative Example 1-6 E-5100 0.15 AO-11) 0.030 at the time of granulation5) good 1.0 P-13) 0.030 Comparative Example 1-7 E-5100 0.10 AO-11) 0.030 at the time of granulation5) could not be press-adhered - P-13) 0.030 Comparative Example 1-8 E-5100 0.15 AO-22) 0.030 at the time of granulation5) good 1.0 P-13) 0.030 Comparative Example 1-9 E-5100 0.10 AO-22) 0.030 at the time of granulation5) could not be press-adhered - P-13) 0.030 1) AO-1: 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-octadecyl propionamide
2) AO-2: n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate
3) P-1: tris(2,4-t-butylphenyl)phosphite
4) at the time of polymerization: the stabilizer was added at the time of polymerizing the monomer having an ethylenically unsaturated bond.
5) at the time of granulation: after the polymerization of the monomer having an ethylenically unsaturated bond, the stabilizer was added and mixed and the resulting mixture was granulated by kneading at 250°C. - According to the results of Comparative Examples 1-1 to 1-9, when a production method different from that of the present invention was employed, the torque increased with time during the extrusion of the polyethylene powder from the T-die, so that a film sheet could not be produced in a stable manner.
- According to the results of Comparative Examples 1-6 and 1-8, although the adhesion with the supporting substrate was improved by increasing the amount of the anchor coating agent to 0.15 g/m2, there was a hygienic problem with the ratio of elution being high. In addition, the laminate films were observed to have coloration and fish-eyes.
- In Comparative Examples 1-7 and 1-9, although a film sheet was obtained, since detachment of the film sheet occurred even when it was press-adhered with the supporting substrate (ester film), a laminate film could not be produced.
- In contrast, from the results of Examples 1-1 to 1-3, it was confirmed that the polyethylene films produced by the production method of the present invention had good adhesion with the supporting substrate (ester film) and the ratio of elution was reduced.
- A laminate film was produced in the same manner as in the above-described Example 1-1, except that the extrusion temperature by T-die was changed as shown in Table 2, that the supporting substrate was changed to an ester film (manufactured by TOYOBO Co., Ltd.; trade name: TOYOBO ESTER FILM T4100), that the anchor coating agent was not used, and that an air having an ozone concentration of 12.9 g/m3 was blown against a surface of the film sheet extruded from the T-die, which surface was press-adhered to the supporting substrate, in an amount of 3 Nm3 per hour.
[Table 2] Outer member Stabilizer Added amount [parts by mass] Method of addition Extrusion temperature [°C] Adhesion strength [g/15mm] Heat-seal strength [kg/15mm] Ratio of elution Example 2-1 T-4100 AO-11) 0.0150 at the time of polymerization4) 280 168 1.86 0.3 Example 2-2 T-4100 AO-11) 0.0030 at the time of polymerization4) 280 171 2.12 0.2 P-13) 0.0060 Example 2-3 T-4100 AO-11) 0.0030 at the time of polymerization4) 280 165 1.76 0.4 P-13) 0.030 at the time of granulation5) Comparative Example 2-1 T-4100 AO-11) 0.0150 at the time of granulation5) 280 -6) film could not be molded Comparative Example 2-2 T-4100 AO-22) 0.0030 at the time of polymerization4) 280 -6) film could not be molded P-13) 0.0060 at the time of granulation5) Comparative Example 2-3 T-4100 AO-11) 0.0030 at the time of granulation5) 280 -6) film could not be molded P-13) 0.0060 at the time of polymerization4) Comparative Example 2-4 T-4100 AO-22) 0.030 at the time of polymerization 280 -6) film could not be molded P-13) 0.030 Comparative Example 2-5 T-4100 AO-11) 0.0030 at the time of granulation5) 280 -6) film could not be molded P-13) 0.0060 Comparative Example 2-6 T-4100 AO-11) 0.030 at the time of granulation5) 280 83 1.32 1.0 P-13) 0.030 Comparative Example 2-7 T-4100 AO-11) 0.030 at the time of granulation5) 300 163 2.21 1.0 P-13) 0.030 Comparative Example 2-8 T-4100 AO-22) 0.030 at the time of granulation5) 280 80 1.21 1.0 P-13) 0.030 Comparative Example 2-9 T-4100 AO-22) 0.030 at the time of granulation5) 300 160 2.02 1.0 P-13) 0.030 6) A film could not be molded, so that the adhesion strength was not evaluated. - According to the results of the above-described Comparative Examples 2-1 to 2-5, when a production method different from that of the present invention was employed, the torque increased with time during the extrusion of the polyethylene powder from the T-die, so that a film sheet could not be produced in a stable manner. Further, from the results of Comparative Examples 2-6 to 2-9, it was confirmed that, although a film sheet could be produced by increasing the amount of the stabilizer composition added in the addition step, the adhesion was defective and the ratio of elution was high, so that there was a hygienic problem. Moreover, from the results of Comparative Examples 2-7 and 2-9, it was confirmed that, although the adhesion was improved by increasing the extrusion temperature to 300°C, there was a hygienic problem with the ratio of elution being high.
- In contrast, from the results of Examples 2-1 to 2-3, it was confirmed that the polyethylene films produced by the production method of the present invention had good adhesion with the supporting substrate (ester film) and the ratio of elution was reduced.
- A laminate film was produced in the same manner as in the above-described Example 1-1 (production of laminate film), except that the anchor coating agent was changed to an adhesive for dry lamination (manufactured by Takeda Pharmaceutical Company Limited trade name: A-515/A-50) and that the extrusion temperature by the T-die was changed from 250°C to 280°C.
[Table 3] Outer member Amount of applied adhesive [g/m2] Stabilizer Added amount [parts by mass] Method of addition Adhesion Ratio of eluted additive amount Example 3-1 E-5100 1.2 AO-11) 0.0150 at the time of polymerization4) good 0.6 Example 3-2 E-5100 1.2 AO-11) 0.0030 at the time of polymerization4) good 0.4 P-13) 0.0060 Example 3-3 E-5100 1.2 AO-11) 0.0030 at the time of polymerization4) good 0.7 P-13) 0.030 at the time of granulation5) Comparative Example 3-1 E-5100 1.2 AO-11) 0.0150 at the time of granulation5) film could not be molded Comparative Example 3-2 E-5100 1.2 AO-22) 0.0030 at the time of polymerization4) film could not be molded P-13) 0.0060 at the time of granulation5) Comparative Example 3-3 E-5100 1.2 AO-11) 0.0030 at the time of granulation5) film could not be molded P-13) 0.0060 at the time of polymerization4) Comparative Example 3-4 E-5100 1.2 AO-22) 0.030 at the time of polymerization film could not be molded P-13) 0.030 Comparative Example 3-5 E-5100 1.2 AO-11) 0.0030 at the time of granulation5) film could not be molded P-13) 0.0060 Comparative Example 3-6 E-5100 2.0 AO-11) 0.030 at the time of granulation5) good 1.0 P-13) 0.030 Comparative Example 3-7 E-5100 1.2 AO-11) 0.030 at the time of granulation5) could not be press-adhered - P-13) 0.030 Comparative Example 3-8 E-5100 2.0 AO-22) 0.030 at the time of granulation5) good 1.0 P-13) 0.030 Comparative Example 3-9 E-5100 1.2 AO-22) 0.030 at the time of granulation5) could not be press-adhered - P-13) 0.030 - According to the results of the above-described Comparative Examples 3-1 to 3-5, when a production method different from that of the present invention was employed, the torque increased with time during the extrusion of the polyethylene powder from the T-die, so that a film sheet could not be produced in a stable manner. Further, from the results of Comparative Examples 3-7 and 3-9, it was confirmed that, although a film sheet could be produced by increasing the amount of the stabilizer composition added in the addition step, the adhesion was poor and the ratio of elution was high, so that there was a hygienic problem. Moreover, from the results of Comparative Examples 3-6 and 3-8, it was confirmed that, although the adhesion was improved by increasing the amount of the applied adhesive from 1.2 g/m2 to 2.0 g/m2, there was a hygienic problem with the ratio of elution being high.
- In contrast, from the results of Examples 3-1 to 3-3, it was confirmed that the polyethylene films produced by the production method of the present invention had good adhesion with the supporting substrate (ester film) and the ratio of elution was reduced.
- Based on the above, as a packaging material, particularly as a packaging bag, the laminate film according to the present invention has excellent resistance to its content, particularly a liquid matter; therefore, the laminate film according to the present invention can be suitably used as a safer and more hygienic packaging material for food articles, pharmaceutical products and the like.
- In accordance with the following procedures ([1] Preparation of Solid Ti Catalyst Component, [2] Preparation of Phenoxide Solution, [3] Preparation of Phosphite Solution and [4] Polymerization of Propylene), a polypropylene powder was obtained.
- After preparing a homogeneous solution by allowing 4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexyl alcohol to react with heating at 130°C for 2 hours, 1.11 g (7.5 mmol) of phthalic anhydride was added to the thus obtained homogeneous solution and the resulting mixture was further allowed to react with stirring at 130°C for 1 hour, thereby dissolving phthalic anhydride in the homogeneous solution. The thus obtained homogeneous solution was cooled to room temperature and the entire amount thereof was then dropwisely charged to 200 ml (1.8 mol) of titanium tetrachloride, which had been kept at -20°C, over a period of 1 hour. Thereafter, the resultant was heated to 110°C over a period of 4 hours and once the temperature reached 110°C, 2.68 ml (12.5 mmol) of diisobutyl phthalate was added and the resulting mixture was maintained at this temperature for 2 hours under stirring. After completion of the 2-hour reaction, the resulting solids were recovered by hot filtration and resuspended in 200 ml of titanium tetrachloride. Then, the thus obtained suspension was once again allowed to react with heating at 110°C for 2 hours. Thereafter, the resulting solids were recovered again by hot filtration and thoroughly washed with 110°C decane and hexane until no free titanium compound was detected in the washings, thereby obtaining a solid Ti catalyst component. The solid Ti catalyst component synthesized by the above-described production method was stored in the form of a heptane slurry and a portion thereof was taken out and dried and the catalyst composition was analyzed. The solid Ti catalyst component obtained in this manner was determined to have the following composition: 3.1 % by weight of titanium, 56.0% by weight of chlorine, 17.0% by weight of magnesium and 20.9% by weight of isobutyl phthalate.
- In a flask whose atmosphere had been replaced with nitrogen, 10 ml of dry heptane, 54 mg of triethylaluminum and 161 mg of the respective phenolic antioxidant shown in Table 4 were mixed with stirring to mask the phenolic antioxidant, thereby preparing a phenoxide solution having a phenolic antioxidant concentration of 16 mg/mL.
- In a flask whose atmosphere had been replaced with nitrogen, 144 mg of the respective phosphorus-based antioxidant shown in Table 4 and 6 mL of heptane were added and mixed with stirring to prepare a phosphite solution having a phosphorus-based antioxidant concentration of 24 mg/mL.
- To a 2L autoclave whose atmosphere had been replaced with nitrogen, 1.26 mmol of triethylaluminum, the thus obtained phenoxide solution and phosphite solution were added in such a manner to attain the respective formulations of stabilizer composition shown in Table 4. Then, 0.126 mmol of dicyclopentyldimethoxysilane and the heptane slurry of the solid Ti catalyst component (8.4 µmol in terms of Ti) were sequentially added. The atmosphere inside the autoclave was replaced with propylene and hydrogen was introduced at a pressure of 0.12 MPa. Further, propylene was introduced such that the total pressure became 3.82 MPa, thereby performing pre-polymerization at 30°C for 3 minutes. Thereafter, while introducing ethylene at a rate of 0.12 g/min, the temperature of the autoclave was raised to 70°C and the total pressure inside the autoclave was adjusted to 3.82 MPa with propylene to perform polymerization reaction for 1 hour. After cooling the autoclave to 40°C, the polymerization reaction was quenched by adding 15 ml of ethanol. Propylene was purged and the resulting polymer was then dried in vacuum at 40°C for 5 hours to obtain polypropylene powder A.
- It is noted here that the amounts of the blended stabilizer shown in Table 4 are each an amount (parts by mass) with respect to a total of 100 parts by mass of the polymer obtained from the monomer having an ethylenically unsaturated bond and the thermoplastic elastomer. Further, the amounts of the blended antioxidant shown in Table 4 are each an amount of the antioxidant by itself prior to being masked. In cases where a stabilizer was added at the time of polymerizing to produce a thermoplastic elastomer, the amount of the blended stabilizer in the whole resin composition is a total of the amount added at the time of polymerizing a monomer having an ethylenically unsaturated bond to produce a polymer and the amount at the time of polymerizing to produce a thermoplastic elastomer. This also applies to the following Production Examples in the same manner.
- Polypropylene powder B was obtained in the same manner as in the above-described Production Example 1, except that neither the phenoxide solution nor the phosphite solution was added.
- In accordance with the following procedures, ([1] Preparation of Solid Catalyst, [2] Preparation of Phenoxide Solution and [3] Polymerization), a thermoplastic elastomer A was obtained.
- In 100 mL of toluene, 37.5 g (0.15 mol) of fine powdery CuSO4·5H2O was suspended at 20°C with stirring and a mixed solution of 50 mL (0.52 mol) of trimethylaluminum and 150 mL of toluene was slowly added thereto dropwise. After completion of the dropwise addition, the resultant was allowed to react at 20°C for another 48 hours. Then, after filtering the reaction solution to remove solid copper sulfate, toluene and unreacted trimethylaluminum were removed by vacuum distillation at a pressure of 266.6 Pa and a temperature of 35°C, thereby obtaining methylaluminoxane in an amount of 17 g (0.29 mol).
- To 2 L of hot water at about 95°C, 500 g of a high-purity γ-alumina (manufactured by JGC Catalysts and Chemicals Ltd, trade name: ACP-1; average particle size: about 60 µm; specific surface area: about 300 m2/g; pore volume: about 0.7 mL/g) was added, and the resulting mixture was stirred for 3 hours, followed by removal of the water. After repeating these operations 10 more times, the resultant was washed with acetone and then dried. The thus dried alumina was heated at 450°C for 6 hours under dry nitrogen gas flow to remove the adsorbed water.
- This alumina in an amount of 7 g was suspended in 50 mL of n-hexane and 82 mg (1.4 mmol in terms of aluminum unit) of methylaluminoxane dissolved in 10 mL of toluene was added to the resulting suspension. After stirring the thus obtained mixture at room temperature for 30 minutes, 9 mL of 0.16M solution of tetrabenzylzirconium dissolved in toluene was added, and the resultant was stirred at room temperature for another 30 minutes. Neither zirconium nor aluminum was detected in the liquid phase.
- As a result of calculation based on the amounts of the adsorbed zirconium and aluminum, the solid catalyst prepared in this manner was found to contain 0.2 mmol/g of zirconium and 0.2 mmol/g of aluminum.
- To 50 ml of toluene, a total of 5.0 g of triisobutylaluminum and the stabilizer(s) (phenolic antioxidant(s)) shown in Table 4 was added such that the molar ratio of the functional groups became 2:1. The resulting mixture was then stirred at room temperature for 30 minutes to prepare a phenoxide solution.
- To a 100L stainless-steel autoclave, hydrogen and ethylene were charged under a nitrogen atmosphere at 25°C such that the hydrogen partial pressure and the ethylene partial pressure became 0.059 MPa and 0.29 MPa, respectively, and 25 kg of propylene was further charged thereto. The temperature of the autoclave was raised to 50°C and, using a pressure equalizer, a heptane slurry of the solid Ti catalyst component (3 mmol in terms of zirconium) was added. Then, after adding the phenoxide solution prepared in the above such that the amount of the added stabilizer(s) in the resulting polymer became as shown in Table 4, ethylene was fed to perform copolymerization for 2 hours while maintaining a temperature of 60°C and a total pressure of 2.84 MPa. Thereafter, the polymerization reaction was quenched by adding 50 mL of isopropyl alcohol. Unreacted propylene was removed and the polymerization product was recovered to obtain a white spherical thermoplastic elastomer A.
- A thermoplastic elastomer B was obtained in the same manner as in the above-described Production Example 3, except that no phenoxide solution was added.
- To 100 parts by mass of a mixture obtained by mixing the polypropylene powder obtained in the above-described Production Example 1 or 2 and the thermoplastic elastomer obtained in the above-described Production Example 3 or 4 at a weight ratio of 2/1 or 4/1, 0.05 parts by mass of calcium stearate, 10 parts by mass of talc (manufactured by NIPPON TALC Co., Ltd.; trade name: MICRO ACE P-4) and 0.2 parts by mass of a light stabilizer (manufactured by ADEKA Corporation; trade name: ADEKA STAB LA-62) were added and mixed. It is noted here that, when the polypropylene powder obtained in Production Example 2 or the elastomer obtained in Production Example 4 was used, the stabilizer composition shown in Table 4 was also added and mixed. Then, the resulting mixture was melt-kneaded using a biaxial extruder (LABO-PLASTOMILL MICRO, manufactured by Toyo Seiki Seisaku-sho, Ltd.) at a melting temperature of 230°C and a screw speed of 50 rpm to obtain a pellet.
- The thus obtained pellet was injection-molded using a laboratory micro-injection molding machine (manufactured by DSM Xplore; Compounder 15, Injection molder 12) at an injection temperature of 220°C and a die temperature of 50°C, thereby preparing a tabular test piece of 50 mm × 90 mm × 2 mm. After the injection molding, the thus obtained test piece was left to stand for 48 hours in a 23°C incubator and then subjected to the following measurements. The results thereof were evaluated by the following procedures.
- The thus obtained test piece was exposed to a saturated vapor of 1,1,1-trichloroethane for 30 seconds and the surface was washed. Then, the resulting test piece was dried for 10 minutes in an oven whose temperature was set at 90°C and subsequently subjected to a plasma treatment using a microwave plasma treatment apparatus (BH-10, manufactured by NISSIN Inc.).
- After the plasma treatment, the test piece was painted with acryl-melamine-type pearl mica in accordance with the following procedures (1) to (7). The painting was performed by using R320, R331 and R341 (trade names; manufactured by Nippon Bee Chemical Co., Ltd.), with R320 (trade name; manufactured by Nippon Bee Chemical Co., Ltd.) being a color base, R331 (trade name; manufactured by Nippon Bee Chemical Co., Ltd.) being a mica base and R341 (trade name; manufactured by Nippon Bee Chemical Co., Ltd.) being a clear paint.
-
- (1) Color base painting, at a film thickness of 15 µm
- (2) After 5-minute setting, drying at 120°C for 20 minutes
- (3) Mica base painting, at a film thickness of 15 µm
- (4) 3-minute flushing
- (5) Clear painting, at a film thickness of 25 µm
- (6) After 5-minute setting, bake-finishing at 120°C for 20 minutes
- (7) Leaving to stand at room temperature for 48 hours
- The test piece thus painted with the acryl-melamine-type pearl mica by the above-described procedures was immersed in 40°C water for 240 hours. Then, using a cutter knife, incisions were made on the paint coating film in a grid form to separate it into 100 1-mm square sections, and a cellophane tape was pasted thereon. The cellophane tape was removed and the number of sections that were not removed by the cellophane tape was measured to evaluate the adhesion of the coating film.
- Further, the above-described test piece painted with the acryl-melamine-type pearl mica was left to stand in a 90°C incubator for 240 hours. Then, the change in the yellowness of the coating film before and after heating (Δb) was measured to evaluate the heat-yellowing resistance. The measurement was performed by using a spectrocolorimeter (model: T-4, manufactured by Suga Test Instruments Co., Ltd.).
- To a pressure-resistant reaction vessel, 215 ml of 95% ethanol aqueous solution was loaded as an extraction solvent. The reaction vessel was hermetically sealed and left to stand for 1 day in a 121°C incubator and a 49°C incubator. After confirming that the temperature of the extraction solvent had reached 121°C, three of the above-described test pieces, which were skewered with a glass rod, were immersed in the extraction solvent in such a manner that the test pieces did not float. Then, the reaction vessel was returned to the 121°C incubator and left to stand therein for 2 hours.
- After the 2-hour incubation, the test pieces were taken out and the surfaces thereof were washed with fresh extraction solvent. Then, the three test pieces were again skewered with a glass rod and immersed in the extraction solvent in the pressure-resistant reaction vessel which had been left to stand in the 49°C incubator. The reaction vessel was hermetically sealed, returned to the 49°C incubator and left to stand therein for 10 days. After the 10-day incubation, the test pieces were taken out and the surfaces thereof were washed with fresh extraction solvent. The extraction solvents used in the 121°C and 49°C incubators and the extraction solvents used in the washing operations were recovered and concentrated under reduced pressure using a rotary evaporator.
- The amount of the stabilizer composition extracted in each of the thus concentrated extraction solvents was quantitatively analyzed by the following method.
- Using gas chromatography [apparatus: Gas Chromatography GC2010, manufactured by Shimadzu Corporation, column: BPX5 manufactured by SGE Analytical Science Pty Ltd. (30 m × 0.25 mmID × 0.25 µm), injection temperature: 330°C, detector temperature: 330°C, measurement condition: heating rate = 15°C/min], the respective blended additives were dissolved in chloroform and a calibration curve was prepared to quantitatively analyze the additive extracted in 95% ethanol aqueous solution. The term "extracted amount" represents a concentration per unit amount of the extraction solvent.
[Table 4] Example 4-1 Example 4-2 Example 4-3 Example 4-4 Additive formulation Composition of polypropylene powder Polypropylene powder A 67 67 80 80 Polypropylene powder B - - - - AO-11) 0.02 0.0067 0.024 0.008 AO-22) - - - - AO-33) - - - - P-14) - 0.03 - 0.03 Method of addition5) at the time of polymerization at the time of polymerization at the time of polymerization at the time of polymerization Composition of elastomer Elastomer A 33 33 20 20 Elastomer B - - - - AO-11) 0.01 0.0033 0.006 0.002 AO-22) - - - - AO-33) - - - - Method of addition5) at the time of polymerization at the time of polymerization at the time of polymerization at the time of polymerization Other Talc6) 10 10 10 10 LA-627) 0.2 0.2 0.2 0.2 Ca-St8) 0.05 0.05 0.05 0.05 Evaluation Secondary adhesion with coating film 100/100 100/100 100/100 100/100 Heat-yellowing resistance (Δb) 0.35 0.28 0.42 0.34 Ratio of elution9) 0.3 0.3 0.3 0.3 Note - - - - 1) AO-1 (phenolic antioxidant): 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-octadecyl propionamide
2) AO-2 (phenolic antioxidant): tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane
3) AO-3 (phenolic antioxidant): n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate
4) P-1 (phosphorus-based antioxidant): tris(2,4-di-tert-butylphenyl)phosphite
5) Method of addition: at the time of polymerization: the antioxidant was added at the time of polymerizing the monomer. at the time of granulation: after the polymerization of the monomer, the antioxidant was added and mixed and the resulting mixture was granulated by kneading at 250°C.
6) Talc: manufactured by NIPPON TALC Co., Ltd.; trade name: MICRO ACE P-4
7) LA-62: light stabilizer, manufactured by ADEKA Corporation; trade name (an ester compound between 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidyltridecyl)
8) Ca-St: calcium stearate
9) Ratio of elution: represents the ratio of the amount of the eluted antioxidant in the respective formulations, taking the amount of the eluted antioxidant in Comparative Example 4-4 as 1.[Table 5] Comparative Example 4-1 Comparative Example 4-2 Comparative Example 4-3 Comparative Example 4-4 Comparative Example 4-5 Additive formulation Composition of polypropylene powder Polypropylene powder A 67 67 - - - Polypropylene powder B - - 67 67 67 AO-11) - - - - - AO-22) 0.2 - 0.02 0.2 0.067 AO-33) - 0.2 - - - P-14) - - - - 0.3 Method of addition5) at the time of polymerization at the time of polymerization at the time of granulation at the time of granulation at the time of granulation Composition of elastomer Elastomer A 33 33 - - - Elastomer B - - 33 33 33 AO-11) - - - - - AO-22) 0.1 - 0.01 0.1 0.033 AO-33) - 0.1 - - - Method of addition5) at the time of polymerization at the time of polymerization at the time of granulation at the time of granulation at the time of granulation Other Talc6) 10 10 10 10 10 LA-627) 0.2 0.2 0.2 0.2 0.2 Ca-St8) 0.05 0.05 0.05 0.05 0.05 Evaluation Secondary adhesion with coating film NG NG NG 95/100 91/100 Heat-yellowing resistance (Δb) NG NG NG 2.02 1.21 Ratio of elution9) NG NG NG 1.0 1.2 Note Deterioration of resin during molding Deterioration of resin during molding Deterioration of resin during molding - - [Table 6] Comparative Example 4-6 Comparative Example 4-7 Comparative Example 4-8 Comparative Example 4-9 Comparative Example 4-10 Additive formulation Composition of polypropylene powder Polypropylene powder A - - - - - Polypropylene powder B 67 67 67 67 67 AO-11) - - - 0.02 0.0067 AO-22) - - - - - AO-33) 0.02 0.2 0.067 - - P-14) - - 0.3 - 0.3 Method of addition5) at the time of granulation at the time of granulation at the time of granulation at the time of granulation at the time of granulation Composition of elastomer Elastomer A - - - - - Elastomer B 33 33 33 33 33 AO-11) - - - 0.01 0.0033 AO-22) - - - - - AO-33) 0.01 0.1 0.033 - - Method of addition5) at the time of granulation at the time of granulation at the time of granulation at the time of granulation at the time of granulation Other Talc6) 10 10 10 10 10 LA-627) 0.2 0.2 0.2 0.2 0.2 Ca-St8) 0.05 0.05 0.05 0.05 0.05 Evaluation Secondary adhesion with coating film NG 92/100 89/100 NG NG Heat-yellowing resistance (Δb) NG 1.72 1.02 NG NG Ratio of elution9) NG 1.0 1.2 NG NG Note Deterioration of resin during molding - - Deterioration of resin during molding Deterioration of resin during molding - According to the results of Comparative Examples 4-1 and 4-2 shown in Table 5, when a phenolic antioxidant different from the one represented by the Formula (1) was added at the time of polymerizing the polypropylene or elastomer and the resultant was then molded, the resulting polypropylene resin and elastomer were deteriorated, so that a test piece could not be prepared.
- Further, according to the results of Comparative Examples 4-3, 4-6, 4-9 and 4-10, when the amount of the antioxidant added at the time of the granulation step was 0.03 parts by mass, the resulting resin was deteriorated during the molding process, so that a test piece could not be prepared.
- Moreover, according to the results of Comparative Examples 4-4, 4-5, 4-7 and 4-8, although the heat resistance was improved by increasing the amount of the antioxidant, the resulting molded articles were markedly colored and had a hygienic problem with the ratio of elution being high, which were not satisfactory.
- In contrast, according to the results of Example 4-1, the coated member of the present invention showed good adhesion with a coating film and good heat-yellowing resistance and had only a small amount of elution. From the results of Example 4-2, it was confirmed that the heat resistance can be further improved by further addition of a phosphorus-based antioxidant.
- Moreover, from the results of Examples 4-3 and 4-4, it was confirmed that there was no problem even when the ratio of the polymer and the thermoplastic elastomer was 4/1 in terms of mass ratio.
-
- 1. A method of producing a laminate film, which is characterized by comprising the step of adding, before or during polymerization of a monomer having an ethylenically unsaturated bond, a phenolic antioxidant represented by the following Formula (1), which is masked with an organoaluminum compound, to at least one of a catalyst system, a polymerization system and a piping, such that said phenolic antioxidant is incorporated in an amount of 0.001 to 0.5 parts by mass with respect to 100 parts by mass of a polymer obtained by said polymerization:
- 2. The method according to clause 1, which further comprises the step of adding, before or during said polymerization of said monomer having an ethylenically unsaturated bond, a phosphorus-based antioxidant to at least one of said catalyst system, said polymerization system and said piping in an amount of 0.001 to 3 parts by mass with respect to 100 parts by mass of said polymer obtained by said polymerization.
- 3. The method according to clause 1, wherein said organoaluminum compound is a trialkylaluminum.
- 4. A laminate film, characterized by being produced by the method according to clause 1.
- 5. A method of producing a resin composition for a coated member, which resin composition comprises a polymer obtained by polymerization of a monomer having an ethylenically unsaturated bond and a thermoplastic elastomer, said method being characterized by comprising the steps of:
- (A) adding, before or during said polymerization of said monomer having an ethylenically unsaturated bond, a phenolic antioxidant represented by the following Formula (1), which is masked with an organoaluminum compound, to at least one of a catalyst system, a polymerization system and a piping, such that said phenolic antioxidant is incorporated in an amount of 0.001 to 0.5 parts by mass with respect to a total of 100 parts by mass of said polymer obtained by said polymerization of said monomer having an ethylenically unsaturated bond and said thermoplastic elastomer; and
- (B) melt-kneading said polymer obtained by said polymerization of said monomer having an ethylenically unsaturated bond with said thermoplastic elastomer:
- 6. The method according to clause 5, wherein, in said step (B), said polymer obtained by polymerization of said monomer having an ethylenically unsaturated bond and said thermoplastic elastomer are melt-kneaded at a mass ratio, said polymer obtained by polymerization of said monomer having an ethylenically unsaturated bond/said thermoplastic elastomer, of 2/1 to 4/1.
- 7. The method according to clause 5, wherein said thermoplastic elastomer is obtained by polymerization of a monomer having an ethylenically unsaturated bond, before or during which polymerization of said monomer having an ethylenically unsaturated bond a phenolic antioxidant represented by said Formula (1), which is masked with an organoaluminum compound, is added to at least one of a catalyst system, a polymerization system and a piping.
- 8. The method according to clause 5, which further comprises the step of adding, before or during said polymerization of said monomer having an ethylenically unsaturated bond, a phosphorus-based antioxidant to at least one of said catalyst system, said polymerization system and said piping, such that said phosphorus-based antioxidant is incorporated in an amount of 0.001 to 3 parts by mass with respect to a total of 100 parts by mass of said polymer obtained by said polymerization of said monomer having an ethylenically unsaturated bond and said thermoplastic elastomer.
- 9. The method according to clause 5, wherein said organoaluminum compound is a trialkylaluminum.
- 10. A method of producing a coated member, which is characterized by comprising the step of coating a molded article of a resin composition obtained by the method according to clause 5.
- 11. The method according to clause 10, which comprises the step of subjecting said molded article of said resin composition to a plasma treatment before said step of coating.
- 12. A coated member, characterized by being produced by the method according to clause 10.
- 13. The coated member according to clause 12, which comprises a light stabilizer and a filler.
Claims (12)
- A method of producing a resin composition for a coated member, which resin composition comprises a polymer obtained by polymerization of a monomer having an ethylenically unsaturated bond and a thermoplastic elastomer, said method being characterized by comprising the steps of:(A) adding, before or during said polymerization of said monomer having an ethylenically unsaturated bond, a phenolic antioxidant represented by the following Formula (1), that is masked with an organoaluminum compound, to at least one of a catalyst system, a polymerization system and a piping, and performing said polymerization such that said phenolic antioxidant is incorporated in an amount of 0.001 to 0.5 parts by mass with respect to a total of 100 parts by mass of said polymer obtained by said polymerization of said monomer having an ethylenically unsaturated bond and said thermoplastic elastomer; and(B) melt-kneading said polymer obtained by said polymerization of said monomer having an ethylenically unsaturated bond with said thermoplastic elastomer:(C) molding the composition from step B into an article.
- The method according to claim 1, wherein, in said step (B), said polymer obtained by polymerization of said monomer having an ethylenically unsaturated bond and said thermoplastic elastomer are melt-kneaded at a mass ratio, said polymer obtained by polymerization of said monomer having an ethylenically unsaturated bond/said thermoplastic elastomer, of 2/1 to 4/1.
- The method according to claim 1, wherein said thermoplastic elastomer is obtained by polymerization of a monomer having an ethylenically unsaturated bond, before or during which polymerization of said monomer having an ethylenically unsaturated bond a phenolic antioxidant represented by said Formula (1), that is masked with an organoaluminum compound, is added to at least one of a catalyst system, a polymerization system and a piping.
- The method according to claim 1, which further comprises the step of adding, before or during said polymerization of said monomer having an ethylenically unsaturated bond, a phosphorus-based antioxidant to at least one of said catalyst system, said polymerization system and said piping, such that said phosphorus-based antioxidant is incorporated in an amount of 0.001 to 3 parts by mass with respect to a total of 100 parts by mass of said polymer obtained by said polymerization of said monomer having an ethylenically unsaturated bond and said thermoplastic elastomer.
- The method according to claim 1, wherein said organoaluminum compound is a trialkylaluminum.
- The method of any of claims 1 to 5, wherein the thermoplastic elastomer is a block copolymer, preferably a copolymer of ethylene and an α-olefin.
- A method of producing a coated member, which is characterized by comprising the step of coating the molded article of a resin composition obtained by the method according to claim 1.
- The method according to claim 7, which comprises the step of subjecting said molded article of said resin composition to a plasma treatment before said step of coating.
- The method according to any preceding claim, wherein said monomer having an ethylenically unsaturated bond is selected from ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcycloalkane, styrene and other α-olefins, preferably ethylene or a combination of α-olefin monomers, more preferably ethylene by itself, a combination of ethylene and propylene, a combination of ethylene, propylene and butene, or a combination of an α-olefin monomer and a non-conjugated diene monomer.
- The method of claim 10, wherein the phenolic antioxidant is compound no. 4.
- A coated member, characterized by being produced by the method according to claim 7, wherein the resin composition comprises a light stabilizer and a filler.
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JP2011045552 | 2011-03-02 | ||
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EP12752936.0A EP2682410B1 (en) | 2011-03-02 | 2012-02-08 | Processes of producing laminate film and resin composition for coating members |
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EP12752936.0A Division EP2682410B1 (en) | 2011-03-02 | 2012-02-08 | Processes of producing laminate film and resin composition for coating members |
EP12752936.0A Division-Into EP2682410B1 (en) | 2011-03-02 | 2012-02-08 | Processes of producing laminate film and resin composition for coating members |
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EP (2) | EP2682410B1 (en) |
JP (1) | JPWO2012117823A1 (en) |
KR (2) | KR20140006018A (en) |
CN (1) | CN103403036B (en) |
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EP2578606B2 (en) | 2011-10-04 | 2019-08-28 | Borealis AG | Process for the production of polyolefins wherein an antioxidant is fed to the reaction mixture during the process |
JP5734826B2 (en) * | 2011-12-20 | 2015-06-17 | 株式会社Adeka | Process for producing olefin resin composition |
JP2013199551A (en) * | 2012-03-23 | 2013-10-03 | Adeka Corp | Method for producing olefin resin composition for home electronic material and automobile interior material |
KR102217316B1 (en) * | 2013-10-21 | 2021-02-17 | 가부시키가이샤 아데카 | Method for producing stabilized polymer |
WO2017115165A1 (en) * | 2016-01-01 | 2017-07-06 | 杭州巨力绝缘材料有限公司 | High-molecular leakage-free self-adhering aluminum foil and preparation method |
CN107571556B (en) * | 2017-09-07 | 2019-07-12 | 山东尚品家居配饰制造有限公司 | A kind of flame retardant decorative film |
CN110854225A (en) * | 2018-07-25 | 2020-02-28 | 比亚迪股份有限公司 | Double-glass photovoltaic assembly |
Citations (55)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4734478A (en) | 1971-03-23 | 1972-11-21 | ||
JPS56100806A (en) | 1980-01-17 | 1981-08-13 | Chisso Corp | Preparation of alpha-olefin polymer |
JPS56120712A (en) | 1980-02-27 | 1981-09-22 | Chisso Corp | Preparation of poly alpha-olefin |
JPS5763310A (en) | 1980-08-13 | 1982-04-16 | Montedison Spa | Ingredient and catalyst for olefin polymerization |
JPS585310A (en) | 1981-07-03 | 1983-01-12 | Mitsubishi Petrochem Co Ltd | Catalytic component for olefin polymerization |
JPS5823806A (en) | 1981-08-04 | 1983-02-12 | Chisso Corp | Preparation of alpha-olefin polymer |
JPS5883006A (en) | 1981-11-13 | 1983-05-18 | Mitsui Petrochem Ind Ltd | Polymerization of olefin |
JPS58104907A (en) | 1981-12-17 | 1983-06-22 | Chisso Corp | Polypropylene for molded article having high rigidity and its preparation |
JPS58157808A (en) | 1982-03-16 | 1983-09-20 | Ube Ind Ltd | Polymerization of alpha-olefin |
JPS61218606A (en) | 1985-03-25 | 1986-09-29 | Sumitomo Chem Co Ltd | Production of alpha-olefin polymer |
JPS61283533A (en) | 1985-06-10 | 1986-12-13 | Mitsubishi Petrochem Co Ltd | Manufacture of metallizing laminated film |
JPS6343915A (en) | 1986-08-11 | 1988-02-25 | Mitsubishi Petrochem Co Ltd | Production of propylene block copolymer |
JPS6349423A (en) | 1986-08-19 | 1988-03-02 | Toppan Printing Co Ltd | Manufacture of laminate |
JPS6383116A (en) | 1986-09-26 | 1988-04-13 | Mitsubishi Petrochem Co Ltd | Production of propylene block copolymer |
JPS6392613A (en) | 1986-07-23 | 1988-04-23 | エニーケム・シンテシース・エセ・ピ・ア | Production of alpha-olefin polymer or copolymer |
JPS63146906A (en) | 1986-09-26 | 1988-06-18 | ソルベイ(ソシエテ アノニム) | Solid catalyst usable in stereospecific polymerization of alpha-olefin |
JPH01246582A (en) | 1988-02-12 | 1989-10-02 | American Bank Note Holographic Inc | Manufacture of discontinuous hologram and article having discontinuous hologram |
JPH0543616A (en) | 1991-08-20 | 1993-02-23 | Mitsubishi Petrochem Co Ltd | Catalyst for olefin polymerization |
JPH05295022A (en) | 1992-04-23 | 1993-11-09 | Mitsubishi Kasei Corp | Catalyst for polymerizing olefin and production of olefin polymer |
JPH05301917A (en) | 1991-05-01 | 1993-11-16 | Mitsubishi Kasei Corp | Olefin-polymerization catalyst and production of olefin polymer using the catalyst |
JPH06107897A (en) | 1992-09-25 | 1994-04-19 | Ube Ind Ltd | Polypropylene resin composition for coated |
JPH06239914A (en) | 1993-02-19 | 1994-08-30 | Mitsubishi Petrochem Co Ltd | Catalyst component for polymerizing alpha-olefin and production of alpha-olefin polymer |
JPH06239917A (en) | 1993-02-19 | 1994-08-30 | Mitsubishi Petrochem Co Ltd | Catalyst component for polymerizing alpha-olefin and production of alpha-olefinic polymer |
JPH06239915A (en) | 1993-02-19 | 1994-08-30 | Mitsubishi Petrochem Co Ltd | Catalyst component for polymerizing alpha-olefin and production of alpha-olefinic polymer |
JPH0782311A (en) | 1993-09-10 | 1995-03-28 | Mitsubishi Chem Corp | Olefin polymerization catalyst and production of olefin polymer using the same |
JPH07179719A (en) | 1993-12-24 | 1995-07-18 | Mitsui Petrochem Ind Ltd | Propylene polymer composition for automotive coated bumper |
JPH07228621A (en) | 1994-02-21 | 1995-08-29 | Mitsubishi Chem Corp | Catalyst for olefin polymerization and polymerization of olefin using the same |
JPH07330820A (en) | 1994-06-10 | 1995-12-19 | Chisso Corp | Cross-linked type metallocene compound and its production |
JPH0859724A (en) | 1994-08-17 | 1996-03-05 | Mitsubishi Chem Corp | Catalyst component for polymerizing alpha-olefin and production of alpha-olefin polymer using the same |
JPH0885707A (en) | 1994-07-22 | 1996-04-02 | Mitsubishi Chem Corp | Catalyst component for polymerizing alpha-olefin and production of alpha-olefin polymer using the same |
JPH0885708A (en) | 1994-07-22 | 1996-04-02 | Mitsubishi Chem Corp | Catalyst component for polymerizing alpha-olefin and production of alpha-olefin polymer using the same |
JPH08127613A (en) | 1994-05-18 | 1996-05-21 | Mitsubishi Chem Corp | Catalyst for polymerizing olefin and method for polymerizing olefin |
JPH08208731A (en) | 1994-11-03 | 1996-08-13 | Ciba Geigy Ag | Preparation of stabilized olefin polymer |
JPH0912621A (en) | 1995-06-29 | 1997-01-14 | Ciba Geigy Ag | Production of stabilized olefin polymer |
JPH10226712A (en) | 1996-12-09 | 1998-08-25 | Mitsubishi Chem Corp | Catalyst for polymerization of alpha-olefin and production of alpha-olefin polymer |
JPH10259143A (en) | 1996-07-23 | 1998-09-29 | Mitsubishi Chem Corp | Purification of metallocene compounds and polymerization of alfa-olefin |
JPH10265490A (en) | 1997-01-21 | 1998-10-06 | Mitsubishi Chem Corp | Each production of silicon-or germaniumcontaining organic compound, transition metal complex, catalyst for polymerizing alpha-olefin and alpha-olefin polymer |
WO1999037654A1 (en) | 1998-01-27 | 1999-07-29 | Chisso Corporation | Metallocene compounds having bis(naphthylcyclo pentadienyl) ligand and process for producing the same |
WO1999045014A1 (en) | 1998-03-05 | 1999-09-10 | Chisso Corporation | Metallocene compounds having bis(2,5-disubstituted-3-phenylcyclopentadienyl) ligand and process for producing the same |
JPH11279189A (en) | 1998-01-27 | 1999-10-12 | Chisso Corp | Metallocene compound having bis(2-substituted-4-phenyl-cyclopentadienyl) ligand, and its production |
JPH11349633A (en) | 1998-06-08 | 1999-12-21 | Mitsubishi Chemical Corp | Novel transition metal compound, catalyst component for olefin polymerization, and production of alpha-olefin polymer |
WO2000008036A1 (en) | 1998-08-03 | 2000-02-17 | Chisso Corporation | ν-OXOBISMETALLOCENE COMPLEXES, CATALYST FOR OLEFIN POLYMERIZATION CONTAINING THE SAME, AND POLYMERIZATION METHOD |
JP2000229990A (en) | 1999-02-15 | 2000-08-22 | Chisso Corp | Metallocene compound containing bis(2,5-disubstituted-3- naphthylcyclopentadienyl) ligand and its production |
JP2001206914A (en) | 2000-01-27 | 2001-07-31 | Japan Polychem Corp | Method for producing propylenic random copolymer |
JP2002037795A (en) | 1999-10-22 | 2002-02-06 | Chisso Corp | Metallocene compound having indenyl ligand and catalyst containing the same and used for polymerizing olefin |
JP2002194016A (en) | 2000-05-23 | 2002-07-10 | Chisso Corp | Metallocene compound, catalyst for olefin polymerization containing the same, and method for producing olefin polymer using the catalyst |
JP2002194015A (en) | 2000-12-25 | 2002-07-10 | Chisso Corp | Catalyst for producing olefin polymer and method for producing olefin polymer using the same |
JP2002535339A (en) | 1999-01-25 | 2002-10-22 | チッソ株式会社 | Metallocene compounds as catalyst components for olefin polymerization |
JP2003029270A (en) | 2001-07-17 | 2003-01-29 | Toshiba Corp | Liquid crystal display device and method of manufacturing liquid crystal display device |
JP2005206625A (en) | 2004-01-20 | 2005-08-04 | Asahi Denka Kogyo Kk | Manufacturing method of stabilized polymer |
JP2005255953A (en) | 2004-03-15 | 2005-09-22 | Asahi Denka Kogyo Kk | Manufacturing method for stabilized polymer |
JP2006052241A (en) | 2004-08-09 | 2006-02-23 | Asahi Denka Kogyo Kk | Method for producing stabilized polymer |
JP2006282985A (en) | 2005-03-11 | 2006-10-19 | Adeka Corp | Production method for stabilized polymer |
WO2010087064A1 (en) * | 2009-01-28 | 2010-08-05 | 株式会社Adeka | Polyolefin-based resin composition for food, medical, and municipal water pipe applications |
EP2281825A1 (en) * | 2008-06-05 | 2011-02-09 | Adeka Corporation | Aluminum phenoxides and process for production of stabilized polymers by using the aluminum phenoxides |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10273544A (en) * | 1997-01-30 | 1998-10-13 | Mitsui Chem Inc | Coated thermoplastic resin composition and coated elastomer composition |
JP4200538B2 (en) | 1998-02-27 | 2008-12-24 | チッソ株式会社 | Metallocene compounds having bis-substituted cyclopentadienyl ligands |
JP2004154942A (en) * | 2002-11-01 | 2004-06-03 | Taka Plastic Navi Kk | Polyethylene sheet and its manufacturing method |
JP4820550B2 (en) * | 2005-01-06 | 2011-11-24 | フタムラ化学株式会社 | Polyolefin film for retort food |
JP2010180390A (en) * | 2009-02-03 | 2010-08-19 | Toyo Adl Corp | Hot-melt type adhesion composition and laminate obtained by using the same |
-
2012
- 2012-02-08 JP JP2013502226A patent/JPWO2012117823A1/en active Pending
- 2012-02-08 EP EP12752936.0A patent/EP2682410B1/en not_active Not-in-force
- 2012-02-08 US US14/002,525 patent/US20130331515A1/en not_active Abandoned
- 2012-02-08 EP EP15181294.8A patent/EP2966095B1/en not_active Not-in-force
- 2012-02-08 BR BR112013022263-8A patent/BR112013022263B1/en active IP Right Grant
- 2012-02-08 KR KR1020137023083A patent/KR20140006018A/en not_active Application Discontinuation
- 2012-02-08 KR KR1020187018690A patent/KR101966269B1/en active IP Right Grant
- 2012-02-08 WO PCT/JP2012/052887 patent/WO2012117823A1/en active Application Filing
- 2012-02-08 CN CN201280011331.4A patent/CN103403036B/en not_active Expired - Fee Related
- 2012-02-24 TW TW101106277A patent/TWI614271B/en not_active IP Right Cessation
Patent Citations (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4734478A (en) | 1971-03-23 | 1972-11-21 | ||
JPS56100806A (en) | 1980-01-17 | 1981-08-13 | Chisso Corp | Preparation of alpha-olefin polymer |
JPS56120712A (en) | 1980-02-27 | 1981-09-22 | Chisso Corp | Preparation of poly alpha-olefin |
JPS5763310A (en) | 1980-08-13 | 1982-04-16 | Montedison Spa | Ingredient and catalyst for olefin polymerization |
JPS585310A (en) | 1981-07-03 | 1983-01-12 | Mitsubishi Petrochem Co Ltd | Catalytic component for olefin polymerization |
JPS5823806A (en) | 1981-08-04 | 1983-02-12 | Chisso Corp | Preparation of alpha-olefin polymer |
JPS5883006A (en) | 1981-11-13 | 1983-05-18 | Mitsui Petrochem Ind Ltd | Polymerization of olefin |
JPS58104907A (en) | 1981-12-17 | 1983-06-22 | Chisso Corp | Polypropylene for molded article having high rigidity and its preparation |
JPS58157808A (en) | 1982-03-16 | 1983-09-20 | Ube Ind Ltd | Polymerization of alpha-olefin |
JPS61218606A (en) | 1985-03-25 | 1986-09-29 | Sumitomo Chem Co Ltd | Production of alpha-olefin polymer |
JPS61283533A (en) | 1985-06-10 | 1986-12-13 | Mitsubishi Petrochem Co Ltd | Manufacture of metallizing laminated film |
JPS6392613A (en) | 1986-07-23 | 1988-04-23 | エニーケム・シンテシース・エセ・ピ・ア | Production of alpha-olefin polymer or copolymer |
JPS6343915A (en) | 1986-08-11 | 1988-02-25 | Mitsubishi Petrochem Co Ltd | Production of propylene block copolymer |
JPS6349423A (en) | 1986-08-19 | 1988-03-02 | Toppan Printing Co Ltd | Manufacture of laminate |
JPS6383116A (en) | 1986-09-26 | 1988-04-13 | Mitsubishi Petrochem Co Ltd | Production of propylene block copolymer |
JPS63146906A (en) | 1986-09-26 | 1988-06-18 | ソルベイ(ソシエテ アノニム) | Solid catalyst usable in stereospecific polymerization of alpha-olefin |
JPH01246582A (en) | 1988-02-12 | 1989-10-02 | American Bank Note Holographic Inc | Manufacture of discontinuous hologram and article having discontinuous hologram |
JPH05301917A (en) | 1991-05-01 | 1993-11-16 | Mitsubishi Kasei Corp | Olefin-polymerization catalyst and production of olefin polymer using the catalyst |
JPH0543616A (en) | 1991-08-20 | 1993-02-23 | Mitsubishi Petrochem Co Ltd | Catalyst for olefin polymerization |
JPH05295022A (en) | 1992-04-23 | 1993-11-09 | Mitsubishi Kasei Corp | Catalyst for polymerizing olefin and production of olefin polymer |
JPH06107897A (en) | 1992-09-25 | 1994-04-19 | Ube Ind Ltd | Polypropylene resin composition for coated |
JPH06239914A (en) | 1993-02-19 | 1994-08-30 | Mitsubishi Petrochem Co Ltd | Catalyst component for polymerizing alpha-olefin and production of alpha-olefin polymer |
JPH06239917A (en) | 1993-02-19 | 1994-08-30 | Mitsubishi Petrochem Co Ltd | Catalyst component for polymerizing alpha-olefin and production of alpha-olefinic polymer |
JPH06239915A (en) | 1993-02-19 | 1994-08-30 | Mitsubishi Petrochem Co Ltd | Catalyst component for polymerizing alpha-olefin and production of alpha-olefinic polymer |
JPH0782311A (en) | 1993-09-10 | 1995-03-28 | Mitsubishi Chem Corp | Olefin polymerization catalyst and production of olefin polymer using the same |
JPH07179719A (en) | 1993-12-24 | 1995-07-18 | Mitsui Petrochem Ind Ltd | Propylene polymer composition for automotive coated bumper |
JPH07228621A (en) | 1994-02-21 | 1995-08-29 | Mitsubishi Chem Corp | Catalyst for olefin polymerization and polymerization of olefin using the same |
JPH08127613A (en) | 1994-05-18 | 1996-05-21 | Mitsubishi Chem Corp | Catalyst for polymerizing olefin and method for polymerizing olefin |
JPH07330820A (en) | 1994-06-10 | 1995-12-19 | Chisso Corp | Cross-linked type metallocene compound and its production |
JPH0885707A (en) | 1994-07-22 | 1996-04-02 | Mitsubishi Chem Corp | Catalyst component for polymerizing alpha-olefin and production of alpha-olefin polymer using the same |
JPH0885708A (en) | 1994-07-22 | 1996-04-02 | Mitsubishi Chem Corp | Catalyst component for polymerizing alpha-olefin and production of alpha-olefin polymer using the same |
JPH0859724A (en) | 1994-08-17 | 1996-03-05 | Mitsubishi Chem Corp | Catalyst component for polymerizing alpha-olefin and production of alpha-olefin polymer using the same |
JPH08208731A (en) | 1994-11-03 | 1996-08-13 | Ciba Geigy Ag | Preparation of stabilized olefin polymer |
JPH0912621A (en) | 1995-06-29 | 1997-01-14 | Ciba Geigy Ag | Production of stabilized olefin polymer |
JPH10259143A (en) | 1996-07-23 | 1998-09-29 | Mitsubishi Chem Corp | Purification of metallocene compounds and polymerization of alfa-olefin |
JPH10226712A (en) | 1996-12-09 | 1998-08-25 | Mitsubishi Chem Corp | Catalyst for polymerization of alpha-olefin and production of alpha-olefin polymer |
JPH10265490A (en) | 1997-01-21 | 1998-10-06 | Mitsubishi Chem Corp | Each production of silicon-or germaniumcontaining organic compound, transition metal complex, catalyst for polymerizing alpha-olefin and alpha-olefin polymer |
WO1999037654A1 (en) | 1998-01-27 | 1999-07-29 | Chisso Corporation | Metallocene compounds having bis(naphthylcyclo pentadienyl) ligand and process for producing the same |
JPH11279189A (en) | 1998-01-27 | 1999-10-12 | Chisso Corp | Metallocene compound having bis(2-substituted-4-phenyl-cyclopentadienyl) ligand, and its production |
WO1999045014A1 (en) | 1998-03-05 | 1999-09-10 | Chisso Corporation | Metallocene compounds having bis(2,5-disubstituted-3-phenylcyclopentadienyl) ligand and process for producing the same |
JPH11349633A (en) | 1998-06-08 | 1999-12-21 | Mitsubishi Chemical Corp | Novel transition metal compound, catalyst component for olefin polymerization, and production of alpha-olefin polymer |
WO2000008036A1 (en) | 1998-08-03 | 2000-02-17 | Chisso Corporation | ν-OXOBISMETALLOCENE COMPLEXES, CATALYST FOR OLEFIN POLYMERIZATION CONTAINING THE SAME, AND POLYMERIZATION METHOD |
JP2002535339A (en) | 1999-01-25 | 2002-10-22 | チッソ株式会社 | Metallocene compounds as catalyst components for olefin polymerization |
JP2000229990A (en) | 1999-02-15 | 2000-08-22 | Chisso Corp | Metallocene compound containing bis(2,5-disubstituted-3- naphthylcyclopentadienyl) ligand and its production |
JP2002037795A (en) | 1999-10-22 | 2002-02-06 | Chisso Corp | Metallocene compound having indenyl ligand and catalyst containing the same and used for polymerizing olefin |
JP2001206914A (en) | 2000-01-27 | 2001-07-31 | Japan Polychem Corp | Method for producing propylenic random copolymer |
JP2002194016A (en) | 2000-05-23 | 2002-07-10 | Chisso Corp | Metallocene compound, catalyst for olefin polymerization containing the same, and method for producing olefin polymer using the catalyst |
JP2002194015A (en) | 2000-12-25 | 2002-07-10 | Chisso Corp | Catalyst for producing olefin polymer and method for producing olefin polymer using the same |
JP2003029270A (en) | 2001-07-17 | 2003-01-29 | Toshiba Corp | Liquid crystal display device and method of manufacturing liquid crystal display device |
JP2005206625A (en) | 2004-01-20 | 2005-08-04 | Asahi Denka Kogyo Kk | Manufacturing method of stabilized polymer |
JP2005255953A (en) | 2004-03-15 | 2005-09-22 | Asahi Denka Kogyo Kk | Manufacturing method for stabilized polymer |
JP2006052241A (en) | 2004-08-09 | 2006-02-23 | Asahi Denka Kogyo Kk | Method for producing stabilized polymer |
JP2006282985A (en) | 2005-03-11 | 2006-10-19 | Adeka Corp | Production method for stabilized polymer |
EP1857468A1 (en) * | 2005-03-11 | 2007-11-21 | Adeka Corporation | Process for production of stabilized polymer |
EP2281825A1 (en) * | 2008-06-05 | 2011-02-09 | Adeka Corporation | Aluminum phenoxides and process for production of stabilized polymers by using the aluminum phenoxides |
WO2010087064A1 (en) * | 2009-01-28 | 2010-08-05 | 株式会社Adeka | Polyolefin-based resin composition for food, medical, and municipal water pipe applications |
EP2392616A1 (en) * | 2009-01-28 | 2011-12-07 | Adeka Corporation | Polyolefin-based resin composition for food, medical, and municipal water pipe applications |
Also Published As
Publication number | Publication date |
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TWI614271B (en) | 2018-02-11 |
BR112013022263A2 (en) | 2016-12-06 |
TW201247714A (en) | 2012-12-01 |
KR20140006018A (en) | 2014-01-15 |
EP2682410B1 (en) | 2015-10-07 |
CN103403036A (en) | 2013-11-20 |
EP2682410A4 (en) | 2014-08-27 |
US20130331515A1 (en) | 2013-12-12 |
JPWO2012117823A1 (en) | 2014-07-07 |
EP2682410A1 (en) | 2014-01-08 |
CN103403036B (en) | 2015-11-25 |
KR101966269B1 (en) | 2019-04-05 |
KR20180080351A (en) | 2018-07-11 |
EP2966095B1 (en) | 2017-05-03 |
WO2012117823A1 (en) | 2012-09-07 |
BR112013022263B1 (en) | 2020-12-08 |
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